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Process Systems
Engineering for Biofuels
Development
Wiley Series
in
Renewable Resources
Series Editor:
Christian V. Stevens, Faculty of Bioscience Engineering, Ghent University, Belgium
Titles in the Series:

Wood Modification: Chemical, Thermal and Other Processes
Callum A. S. Hill
Renewables-Based Technology: Sustainability Assessment
Jo Dewulf, Herman Van Langenhove
Biofuels
Wim Soetaert, Erik Vandamme
Handbook of Natural Colorants
Thomas Bechtold, Rita Mussak
Surfactants from Renewable Resources
Mikael Kjellin, Ingegärd Johansson
Industrial Applications of Natural Fibres: Structure, Properties and Technical Applications
Jörg Müssig
Thermochemical Processing of Biomass: Conversion into Fuels, Chemicals and Power
Robert C. Brown
Biorefinery Co-Products: Phytochemicals, Primary Metabolites and Value-Added Biomass
Processing
Chantal Bergeron, Danielle Julie Carrier, Shri Ramaswamy
Aqueous Pretreatment of Plant Biomass for Biological and Chemical Conversion to Fuels and
Chemicals
Charles E. Wyman
Bio-Based Plastics: Materials and Applications
Stephan Kabasci
Introduction to Wood and Natural Fiber Composites
Douglas D. Stokke, Qinglin Wu, Guangping Han
Cellulosic Energy Cropping Systems
Douglas L. Karlen
Introduction to Chemicals from Biomass, 2nd Edition
James H. Clark, Fabien Deswarte
Lignin and Lignans as Renewable Raw Materials: Chemistry, Technology and Applications
Francisco G. Calvo-Flores, Jose A. Dobado, Joaquín Isac-García, Francisco J. Martin-Martínez
Sustainability Assessment of Renewables-Based Products: Methods and Case Studies
Jo Dewulf, Steven De Meester, Rodrigo A. F. Alvarenga
Cellulose Nanocrystals: Properties, Production and Applications
Wadood Hamad
Fuels, Chemicals and Materials from the Oceans and Aquatic Sources
Francesca M. Kerton, Ning Yan
Bio-Based Solvents
François Jérôme and Rafael Luque
Nanoporous Catalysts for Biomass Conversion
Feng-Shou Xiao and Liang Wang
Thermochemical Processing of Biomass: Conversion into Fuels, Chemicals and Power, 2nd
Edition
Robert C. Brown
The Chemical Biology of Plant Biostimulants
Danny Geelen, Lin Xu
Chitin and Chitosan: Properties and Applications
Lambertus A.M. van den Broek and Carmen G. Boeriu
Biorefinery of Inorganics: Recovering Mineral Nutrients from Biomass and Organic Waste
Erik Meers, Evi Michels, Rene Rietra, Gerard Velthof
Process Systems Engineering for Biofuels Development
Adrián Bonilla-Petriciolet, Gade Pandu Rangaiah
Forthcoming Titles:
Waste Valorization: Waste Streams in a Circular Economy
Carol Sze Ki Lin, Chong Li, Guneet Kaur, Xiaofeng Yang
Biobased Packaging: Material, Environmental and Economic Aspects
Mohd Sapuan Salit, Rushdan Ahmad Ilyas
High-Performance Materials from Bio-based Feedstocks
Andrew J. Hunt, Nontipa Supanchaiyamat, Kaewta Jetsrisuparb, Jesper T.N. Knijnenburg
Process Systems
Engineering for Biofuels
Development
Edited by
ADRIÁN BONILLA-PETRICIOLET
Instituto Tecnológico de Aguascalientes, México
GADE PANDU RANGAIAH

National University of Singapore, Singapore
and
Vellore Institute of Technology, India
This edition first published 2020
© 2020 John Wiley & Sons Ltd.
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on how to obtain permission to reuse material from this title is available at http://www.wiley.com/go/permissions.
The right of Adrián Bonilla-Petriciolet and Gade Pandu Rangaiah to be identified as the authors of the editorial material
in this work has been asserted in accordance with law.
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Library of Congress Cataloging-in-Publication Data
Names: Bonilla-Petriciolet, Adrián, editor. | Rangaiah, Gade Pandu, editor.
Title: Process systems engineering for biofuels development / edited by

Adrián Bonilla-Petriciolet, Dept. Chemical Engineering, Instituto
Tecnológico de Aguascalientes, Aguascalientes, México, Gade Pandu Rangaiah,
National University of Singapore, Singapore.
Description: First edition. | Hoboken, NJ : John Wiley & Sons, Inc., [2020]
| Series: Wiley series in renewable resources | Includes bibliographical references and index.
Identifiers: LCCN 2020016306 (print) | LCCN 2020016307 (ebook) | ISBN
9781119580270 (cloth) | ISBN 9781119580317 (adobe pdf) | ISBN
9781119580331 (epub)
Subjects: LCSH: Biomass energy. | Chemical processes. | Systems engineering.
Classification: LCC TP339 .P753 2020 (print) | LCC TP339 (ebook) | DDC
662/.88–dc23
LC record available at https://lccn.loc.gov/2020016306
LC ebook record available at https://lccn.loc.gov/2020016307
Cover Design: Wiley

Cover Image: © Jim Barber/Shutterstock
Set in 10/12pt, TimesLTStd by SPi Global, Chennai, India.
Printed and bound by CPI Group (UK) Ltd, Croydon, CR0 4YY
10 9 8 7 6 5 4 3 2 1
Contents
List of Contributors xiii
Series Preface xv
Preface xvii
1 Introduction 1
Adrián Bonilla-Petriciolet and Gade Pandu Rangaiah
1.1 Importance of Biofuels and Overview of their Production 1
1.2 Significance of Process Systems Engineering for Biofuels
Production 3
1.2.1 Modeling of Physicochemical Properties of
Thermodynamic Systems Related to Biofuels 4
1.2.2 Intensification of the Biomass Transformation Routes for
the Production of Biofuels 5
1.2.3 Computer-Aided Methodologies for Process Modeling,
Design, Optimization, and Control Including Supply Chain
and Life Cycle Analyses 7
1.3 Overview of this Book 9
References 11
2 Waste Biomass Suitable as Feedstock for Biofuels Production 15

Maria Papadaki
2.1 Introduction 15
2.1.1 The Need for Biofuels 15
2.1.2 Problem Definition 17
2.1.3 The Biomass Pool 18
2.2 Kinds of Feedstock 20
2.2.1 Spent Coffee Grounds 21
2.2.2 Lignocellulose Biomass 22
2.2.3 Palm, Olive, Coconut, Avocado, and Argan Oil Production
Residues 25
2.2.4 Citrus 33
2.2.5 Grape Marc 36
viii Contents
2.2.6 Waste Oil and Cooking Oil 37

2.2.7 Additional Sources 38
2.3 Conclusions 40
Acknowledgment 40
References 40
3 Multiscale Analysis for the Exploitation of Bioresources: From Reactor

Design to Supply Chain Analysis 49
Antonio Sánchez, Borja Hernández, and Mariano Martín
3.1 Introduction 49
3.2 Unit Level 50
3.2.1 Short Cut Methods 50
3.2.2 Mechanistic Models 51
3.2.3 Rules of Thumb 56
3.2.4 Dimensionless Analysis 56
3.2.5 Surrogate Models 56
3.2.6 Experimental Correlations 59
3.3 Process Synthesis 60
3.3.1 Heuristic Based 60
3.3.2 Supestructure Optimization 61
3.3.3 Environmental Impact Metrics 65
3.3.4 Safety Considerations 66
3.4 The Product Design Problem 66
3.4.1 Product Design: Engineering Biomass 66
3.4.2 Blending Problems 68
3.5 Supply Chain Level 68
3.5.1 Introduction 68
3.5.2 Modeling Issues 70
3.6 Multiscale Links and Considerations 71
Acknowledgment 74
Nomenclature 74
References 75
4 Challenges in the Modeling of Thermodynamic Properties and Phase

Equilibrium Calculations for Biofuels Process Design 85
Roumiana P. Stateva and Georgi St. Cholakov
4.1 Introduction 85
4.2 Thermodynamic Modeling Framework: Elements, Structure,
and Organization 86
4.3 Thermodynamics of Biofuel Systems 88
4.3.1 Phase Equilibria 88
4.3.2 Thermodynamic Models 90
4.4 Sources of Data for Biofuels Process Design 98
4.5 Methods for Predicting Data for Biofuels Process Design 102
4.5.1 Group Contribution Methods for Biofuels Process Design 103
4.5.2 Quantitative Structure–Property Relationships for Biofuels
Process Design 105
Contents ix
4.6 Challenges for the Biofuels Process Design Methods 109

4.7 Influence of Uncertainties in Thermophysical Properties of Pure
Compounds on the Phase Behavior of Biofuel Systems 112
4.8 Conclusions 114
Acknowledgment 114
Exercises 114
References 115
5 Up-grading of Waste Oil: A Key Step in the Future of Biofuel

Production 121
Luigi di Bitonto and Carlo Pastore
5.1 Introduction 121
5.2 Physicochemical Pretreatments of Waste Oils: Removal of
Contaminants 124
5.3 Direct Treatment and Conversion of FFAs into Methyl Esters 125
5.3.1 Homogeneous Catalysis: Brønsted and Lewis
Acids 125
5.3.2 Heterogeneous Catalysis 127
5.3.3 Enzymatic Biodiesel Production 128
5.3.4 ILs Biodiesel Production 130
5.3.5 Use of Metal Hydrated Salts 133
5.4 Future Trends of the Pretreatments of Waste Oils 139
5.5 Conclusions 140
Acknowledgment 141
Abbreviations 141
References 142
6 Production of Biojet Fuel from Waste Raw Materials: A Review 149

Ana Laura Moreno-Gómez, Claudia Gutiérrez-Antonio, Fernando Israel
Gómez-Castro, and Salvador Hernández
6.2 Waste Triglyceride Feedstock 150
6.3 Waste Lignocellulosic Feedstock 159
6.4 Waste Sugar and Starchy Feedstock 164
6.5 Main Challenges and Future Trends 165
6.6 Conclusions 167
Acknowledgments 167
References 167
7 Computer-Aided Design for Genetic Modulation to Improve Biofuel

Production 173
Feng-Sheng Wang and Wu-Hsiung Wu
7.2 Method 175
7.2.1 Flux Balance Analysis 175
7.2.2 Flux Variability Analysis 176
7.2.3 Minimization of Metabolic Adjustment 176
x Contents
7.2.4 Regulatory On-Off Minimization 177

7.2.5 Optimal Strain Design Problem 177
7.3 Computer-Aided Strain Design Tool 179
7.4 Examples 181
7.4.1 E. coli Core Model 181
7.4.2 Genome-Scale Metabolic Model of E. coli iAF1260 183
7.5 Conclusions 185
Appendix 7.A: The SBP Program 187
References 187
8 Implementation of Biodiesel Production Process Using

Enzyme-Catalyzed Routes 191
Thalles Allan Andrade, Massimiliano Errico, and Knud Villy Christensen
8.2 Biodiesel Production Routes: Chemical versus Enzymatic Catalysts 194
8.2.1 Chemical Catalysts 195
8.2.2 Enzymatic Catalysts 196
8.3 Optimal Reaction Conditions and Kinetic Modeling 198
8.3.1 Evaluation of the Reaction Conditions 199
8.3.2 Kinetic Modeling 201
8.4 Process Simulation and Economic Evaluation 205
8.5 Reuse of Enzyme for the Transesterification Reaction 210
8.5.1 Recovery of Eversa Transform by Means of Centrifugation 210
8.5.2 Recovery of Eversa Transform by Means of Ceramic
Membranes 211
8.6 Environmental Impact and Final Remarks 215
Acknowledgments 217
Nomenclature 217
References 217
9 Process Analysis of Biodiesel Production – Kinetic Modeling,

Simulation, and Process Design 221
Bruna Ricetti Margarida, Wanderson Rogerio Giacomin-Junior,
Luiz Fernando de Lima Luz Junior, Fernando Augusto Pedersen Voll,
and Marcos Lucio Corazza
9.1.1 Homogeneous-Based Reactions 222
9.1.2 Heterogeneous-Based Reactions 223
9.1.3 Enzyme-Catalyzed Reactions 224
9.1.4 Supercritical Route Reactions 224
9.1.5 Methanol or Ethanol for Biodiesel Synthesis 224
9.2 Getting Started with Aspen Plus V10 224
9.2.1 Pure Compounds 225
9.2.2 Mixture Parameters 229
9.3 Kinetic Study 232
9.3.1 Esterification Reaction 232
Contents xi
9.3.2 Experimental Reaction Data Regression 234

9.3.3 Transesterification Reaction 236
9.3.4 Supercritical Route 238
9.4 Process Design 239
9.4.1 Esterification Reaction 239
9.4.2 Methanol Recycling 243
9.4.3 Transesterification Reaction 244
9.4.4 Biodiesel Purification 245
9.4.5 Additional Resources 248
9.5 Energy and Economic Analysis 252
9.6 Concluding Remarks 254
Acknowledgment 255
Exercises 255
References 256
10 Process Development, Design and Analysis of Microalgal Biodiesel

Production Aided by Microwave and Ultrasonication 259
Dipesh S. Patle, Savyasachi Shrikhande, and Gade Pandu Rangaiah
10.2 Process Development and Modeling 262
10.3 Sizing and Cost Analysis 272
10.4 Comparison with the WCO-Based Process of the Same Capacity 277
10.4.1 Biodiesel Process Using WCO as Raw Material 277
10.4.2 Comparative Analysis 277
10.5 Comparison with the Microalgae-Based Processes 280
10.6 Conclusions 280
Acknowledgment 281
Appendix 10.A 281
Exercises 282
References 282
11 Thermochemical Processes for the Transformation of Biomass into

Biofuels 285
Carlos J. Durán-Valle
11.2 Biomass and Biofuels 288
11.3 Combustion 289
11.4 Gasification 290
11.4.1 Fixed Bed Gasification 291
11.4.2 Fluidized Bed Gasification 292
11.4.3 Dual Fluidized Bed Gasification 292
11.4.4 Hydrothermal Gasification 293
11.4.5 Supercritical Water Gasification 294
11.4.6 Plasma Gasification 294
11.4.7 Catalyzed Gasification 295
11.4.8 Fischer–Tropsch Synthesis 295
xii Contents
11.5 Liquefaction 296

11.6 Pyrolysis 296
11.6.1 Slow Pyrolysis 297
11.6.2 Fast Pyrolysis 297
11.6.3 Flash Pyrolysis 297
11.6.4 Catalytic Biomass Pyrolysis 303
11.6.5 Microwave Heating 304
11.6.6 Product Separation 304
11.7 Carbonization 305
Acknowledgments 309
References 309
12 Intensified Purification Alternative for Methyl Ethyl Ketone

Production: Economic, Environmental, Safety and Control Issues 311
Eduardo Sánchez-Ramírez, Juan José Quiroz-Ramírez, and
Juan Gabriel Segovia-Hernández
12.2 Problem Statement and Case Study 316
12.3 Evaluation Indexes and Optimization Problem 317
12.3.1 Total Annual Cost Calculation 319
12.3.2 Environmental Index Calculation 319
12.3.3 Individual Risk Index 320
12.3.4 Controllability Index Calculation 322
12.3.5 Multi-Objective Optimization Problem 323
12.4 Global Optimization Methodology 324
12.5 Results 325
Acknowledgments 335
Notation 335
References 336
13 Present and Future of Biofuels 341

Juan Gabriel Segovia-Hernández, César Ramírez-Márquez, and
Eduardo Sánchez-Ramírez
13.2 Some Representative Biofuels 344
13.2.1 Bioethanol 344
13.2.2 Biodiesel 347
13.2.3 Biobutanol 348
13.2.4 Biojet Fuel 349
13.2.5 Biogas 351
13.3 Perspectives and Future of Biofuels 352
References 354
Index 357
List of Contributors
Thalles Allan Andrade Department of Chemical Engineering, Biotechnology and
Environmental Technology, University of Southern Denmark, Odense M, Denmark
Luigi di Bitonto Istituto di Ricerca Sulle Acque (IRSA), Consiglio Nazionale delle
Ricerche (CNR), Bari, Italy
Adrián Bonilla-Petriciolet Instituto Tecnológico de Aguascalientes, Aguascalientes,
Mexico
Georgi St. Cholakov Department of Organic Synthesis and Fuels, University of
Chemical Technology and Metallurgy, Sofia, Bulgaria
Knud Villy Christensen Department of Chemical Engineering, Biotechnology and
Marcos Lucio Corazza Department of Chemical Engineering, Federal University of
Paraná, Polytechnic Center (DEQ/UFPR), Curitiba, Brazil
Carlos J. Durán-Valle Departamento de Química Orgánica e Inorgánica, Universidad
de Extremadura, Badajoz, Spain
Massimiliano Errico Department of Chemical Engineering, Biotechnology and
Wanderson Rogerio Giacomin-Junior Department of Chemical Engineering, Federal
University of Paraná, Polytechnic Center (DEQ/UFPR), Curitiba, Brazil
Fernando Israel Gómez-Castro Departamento de Ingeniería Química, Universidad de
Guanajuato, Guanajuato, Guanajuato, México
Claudia Gutiérrez-Antonio Facultad de Química, Universidad Autónoma de Querétaro,
Querétaro, Querétaro, México
Borja Hernández Department of Chemical Engineering, University of Salamanca,
Salamanca, Spain
Salvador Hernández Departamento de Ingeniería Química, Universidad de Guanajuato,
Guanajuato, Guanajuato, México
xiv List of Contributors
Luiz Fernando de Lima Luz Junior Department of Chemical Engineering, Federal

Mariano Martín Department of Chemical Engineering, University of Salamanca,
Salamanca, Spain
Ana Laura Moreno-Gómez Facultad de Química, Universidad Autónoma de Querétaro,
Querétaro, Querétaro, México
Maria Papadaki Department of Environmental Engineering, University of Patras,
Agrinio, Greece
Carlo Pastore Istituto di Ricerca Sulle Acque (IRSA), Consiglio Nazionale delle
Ricerche (CNR), Bari, Italy
Dipesh S. Patle Chemical Engineering Department, Motilal Nehru National Institute of
Technology, Allahabad, India
Fernando Augusto Pedersen Voll Department of Chemical Engineering, Federal
Juan José Quiroz-Ramírez CONACyT – CIATEC A.C. Centro de Innovación Aplicada
en Tecnologías Competitivas, León, México
Bruna Ricetti Margarida Department of Chemical Engineering, Federal University of
Paraná, Polytechnic Center (DEQ/UFPR), Curitiba, Brazil
César Ramírez-Márquez Departamento de Ingeniería Química, Universidad de
Gade Pandu Rangaiah Department of Chemical and Biomolecular Engineering,
National University of Singapore, Singapore and School of Chemical Engineering, Vellore
Institute of Technology, Vellore, India
Antonio Sánchez Department of Chemical Engineering, University of Salamanca,
Salamanca, Spain
Eduardo Sánchez-Ramírez Departamento de Ingeniería Química, Universidad de
Juan Gabriel Segovia-Hernández Departamento de Ingeniería Química, Universidad
de Guanajuato, Guanajuato, México
Savyasachi Shrikhande School of Chemical Engineering, VIT, Vellore, India
Roumiana P. Stateva Institute of Chemical Engineering, Bulgarian Academy of
Sciences, Sofia, Bulgaria
Feng-Sheng Wang Department of Chemical Engineering, National Chung Cheng
University, Chiya, Taiwan
Wu-Hsiung Wu Department of Chemical Engineering, National Chung Cheng
University, Chiya, Taiwan
Series Preface
Renewable resources, their use and modification are involved in a multitude of important
processes with a major influence on our everyday lives. Applications can be found in the
energy sector; paints and coatings; and the chemical, pharmaceutical, and textile industry,
to name but a few.
The area interconnects several scientific disciplines (agriculture, biochemistry, chem-
istry, technology, environmental sciences, forestry), which makes it very difficult to have
an expert view on the complicated interaction. Therefore, the idea to create a series of sci-
entific books, focusing on specific topics concerning renewable resources, has been very
opportune and can help to clarify some of the underlying connections in this area.
In a very fast-changing world, trends are not only characteristic of fashion and politi-
cal standpoints; science too is not free from hypes and buzzwords. The use of renewable
resources is again more important nowadays; however, it is not part of a hype or a fashion.
As the lively discussions among scientists continue about how many years we will still be
able to use fossil fuels – opinions ranging from 50 to 500 years – they do agree that the
reserve is limited, and that it is essential not only to search for new energy carriers but also
for new material sources.
In this respect, the field of renewable resources is a crucial area in the search for alterna-
tives for fossil-based raw materials and energy. In the field of energy supply, biomass- and
renewables-based resources will be part of the solution alongside other alternatives such as
solar energy, wind energy, hydraulic power, hydrogen technology and nuclear energy. In the
field of material sciences, the impact of renewable resources will probably be even bigger.
Integral utilization of crops and the use of waste streams in certain industries will grow in
importance, leading to a more sustainable way of producing materials. Although our soci-
ety was much more (almost exclusively) based on renewable resources centuries ago, this
disappeared in the Western world in the nineteenth century. Now it is time to focus again
on this field of research. However, it should not mean a “retour à la nature,” but should be
a multidisciplinary effort on a highly technological level to perform research toward new
opportunities, to develop new crops and products from renewable resources. This will be
essential to guarantee an acceptable level of comfort for the growing number of people liv-
ing on our planet. It is “the” challenge for the coming generations of scientists to develop
more sustainable ways to create prosperity and to fight poverty and hunger in the world. A
global approach is certainly favored.
xvi Series Preface
This challenge can only be dealt with if scientists are attracted to this area and are rec-
ognized for their efforts in this interdisciplinary field. It is, therefore, also essential that
consumers recognize the fate of renewable resources in a number of products. Further-
more, scientists do need to communicate and discuss the relevance of their work. The use
and modification of renewable resources may not follow the path of the genetic engineering
concept in view of consumer acceptance in Europe. Related to this aspect, the series will
certainly help to increase the visibility of the importance of renewable resources. Being
convinced of the value of the renewables approach for the industrial world, as well as for
developing countries, I was myself delighted to collaborate on this series of books focusing
on the different aspects of renewable resources. I hope that readers become aware of the
complexity, the interaction and interconnections, and the challenges of this field, and that
they will help to communicate on the importance of renewable resources.
I certainly want to thank the people of Wiley’s Chichester office, especially David
Hughes, Jenny Cossham and Lyn Roberts, in seeing the need for such a series of books on
renewable resources, for initiating and supporting it, and for helping to carry the project to
the end.
Last, but not least, I want to thank my family, especially my wife Hilde and children
Paulien and Pieter-Jan, for their patience, and for giving me the time to work on the series
when other activities seemed to be more inviting.
Christian V. Stevens,
Faculty of Bioscience Engineering Ghent University, Belgium
Series Editor, “Renewable Resources”
June 2005
Preface
Biofuels (e.g. biodiesel, bioalcohols, and biojet fuel) are alternative energy solutions to the
environmental and safety problems related to the use of petroleum-based fuels. This renew-
able energy can be generated from a wide variety of low-cost feedstocks and transformation
routes that also imply a spectrum of process units based on different technologies. During
the past two decades, significant developments and improvements have been achieved to
increase the commercial production of biofuels worldwide. However, the creation and oper-
ation of sustainable biofuel production chains have imposed new challenges to the field of
Process Systems Engineering (PSE). The analysis, modeling, design, optimization, intensi-
fication, and control of individual units (e.g. reactors and separators) and the entire facilities
to produce biofuels have generated drivers for PSE research and development, which should
be addressed via theoretical, computational, and experimental studies.
The PSE of biofuel production schemes demands advances and novel contributions
to handle the challenges associated with the diversity of physicochemical properties of
available feedstocks, biofuel processing routes, operating conditions, and characteristics
of technologies applied in pretreatment units, reactors, separators, and other process
equipment. The opportunities of PSE in the production of renewable biofuels include
(i) development of a reliable thermodynamic framework for estimating the properties
of pure components and mixtures that are required in the design, control, and intensi-
fication of biomass transformation routes; (ii) intensification and optimization of the
processing routes to handle a wide variety of feedstocks for obtaining biofuels and other
high-value-added by-products; (iii) implementation of realistic and proper models for PSE
analysis; (iv) application of reliable global and multiobjective optimization techniques for
solving design problems and improving the performance of biofuel production schemes;
and (v) utilization of computer-aided methodologies for process controllability, mass
and energy integration, and other tasks associated with PSE. Therefore, theoretical,
computational, and experimental studies in these and other topics are required to develop
a sustainable biofuel production chain.
The present book is the first one specifically devoted to PSE for the production of bio-
fuels. It covers a wide range of topics associated with the process engineering of biofuel
production including the thermodynamic modeling, process design and control, reaction
engineering, separation, and purification of biofuels obtained from different biomass feed-
stocks and transformation routes. In all, this book contains 13 chapters devoted to PSE
xviii Preface
for biofuel production. It provides an overview of the subject and covers the portfolio of
available biomass feedstocks for biofuel production, multiscale analysis of bioresources,
challenges in modeling thermodynamic properties and phase equilibrium calculations, the
production and separation of biofuels, computer-aided design, enzyme-catalyzed biodiesel
production, process analysis of biodiesel production (including kinetic modeling and simu-
lation), and the use of ultrasonification in biodiesel production, as well as thermochemical
processes for biomass transformation and production of alternative biofuels. It is a collec-
tion of contributions from leading researchers in PSE and biofuels. Every chapter in this
book has been reviewed anonymously by at least two experts and then thoroughly revised by
the respective contributors. This review process has been attempted to provide high-quality
and educational value for all chapters.
This book will provide researchers and postgraduate students with an overview of the
recent developments and applications of some state-of-the-art technologies and PSE for bio-
fuel production. We consider that this book is a useful resource for researchers in renewable
energies and practitioners working on the production of biofuels.
We are grateful to all the contributors and reviewers of the chapters for their cooperation
to meet the requirements and schedule to finalize this book. We would like to thank the
book publishing team of John Wiley & Sons, Ltd, for their support and assistance during
the preparation of this book.
Adrián Bonilla-Petriciolet
Instituto Tecnológico de Aguascalientes, México
Gade Pandu Rangaiah
National University of Singapore, Singapore
June 2020
1
Introduction
Adrián Bonilla-Petriciolet1 and Gade Pandu Rangaiah2,3
1
Instituto Tecnológico de Aguascalientes, Aguascalientes 20256, Mexico
2 Department of Chemical and Biomolecular Engineering, National University of Singapore,117585,
Singapore
3
School of Chemical Engineering, Vellore Institute of Technology, Vellore 632014, India
1.1 Importance of Biofuels and Overview of their Production

The relevance and importance of biofuels are recognized worldwide, mainly due to the
problems caused by fossil fuel depletion and environmental pollution (e.g. climate change)
arising from the generation and consumption of traditional energy sources (Li et al. 2019;
Raud et al. 2019; Quiroz-Perez et al. 2019). Biofuels belong to the category of sustainable
energy that can be obtained from biological (e.g. anaerobic digestion and fermentation),
physicochemical (e.g. transesterification), and thermochemical (e.g. liquefaction, gasifica-
tion, and pyrolysis) processing routes, which can involve the application of conventional
and intensified technologies (Gutierrez-Antonio et al. 2017; Li et al. 2019; Quiroz-Perez
et al. 2019). Several researchers have concluded that biomasses can be regarded as a pri-
mary source for obtaining green and renewable energy because they are distributed and
generated worldwide (Li et al. 2019; Quiroz-Perez et al. 2019; Wei et al. 2019). In fact, it
has been estimated that the biomass-based fuel sources can account for 70% of all renewable
energy production (Raud et al. 2019).
Diverse processes have been studied and implemented to perform the transforma-
tion of biomass-based feedstocks to solid, liquid and/or gaseous products that contain
energy-enriched chemicals (Quiroz-Perez et al. 2019). Lignocellulosic materials, food
crops, urban wastes, animal fats, vegetable oils, starch-rich compounds and non-edible
Process Systems Engineering for Biofuels Development, First Edition.

Edited by Adrián Bonilla-Petriciolet and Gade Pandu Rangaiah.
© 2020 John Wiley & Sons Ltd. Published 2020 by John Wiley & Sons Ltd.
2 Process Systems Engineering for Biofuels Development
Table 1.1 Classification of biofuels based on the biomass feedstock and its transformation route.
Type of biofuels according to their processing routes

Primary Secondary
1st generation 2nd generation 3rd generation 4th generation
Firewood, wood, Bioethanol or Bioethanol, Biodiesel or Biofuels produced
pellets, chips, butanol from biobutanol or bioethanol from using genetically
forest and fermentation of synthesized biofuels microalgae, modified
agricultural starch or sugars made from seaweed or microalgae or
residues, gas. contained in food non-food microorganisms. microorganisms.
crops. lignocellulosic
biomass.
Source: Raud et al. 2019. Reproduced with permission of Elsevier.
biomasses like algae and microorganisms (with and without genetic modifications) can
be utilized as feedstocks to produce renewable fuels (Sawangkeaw and Ngamprasertsith
2013; Loman and Ju 2016; Stephen and Periyasamy 2018). Biofuels include end products
known as biodiesel (a mixture of long-chain alkyl esters), biojet fuel (a mixture of C8–C16
alkanes, iso-alkanes, naphthenic derivatives, and aromatic compounds), biogasoline
(C6–C12 hydrocarbons), and bioalcohols (e.g. bioethanol and biobutanol) (Hassan et al.
2015; Gutierrez-Antonio et al. 2017; Wei et al. 2019). Table 1.1 shows a common and
simple classification of biofuels based on the biomass used as the starting material and its
processing route (Raud et al. 2019).
The production of biofuels comprises several process units that should be analyzed, mod-
eled, designed, optimized, intensified, and controlled. In general, conventional processes
employed in biofuels production rely on unit operations that are performed independently
without mass and/or energy integration, whose process conditions are not optimized and the
tradeoff between process efficiency and cost may not be the best (Quiroz-Perez et al. 2019).
On the other hand, intensified process operations outperform their conventional counter-
parts in terms of energy consumption, profitability, and effectiveness. Process intensifica-
tion generally reduces the equipment number, sizes and/or energy consumption, to increase
the productivity and to enhance other performance metrics via the synergy obtained from
multifunctional phenomena at different spatial and time scales (Stankiewicz and Moulijn
2000; Tian et al. 2018). It allows the integration of two or more operations in multitask-
ing units, the development of alternative configurations and design of process equipment,
besides the application of optimization tools and reliable process synthesis methodologies
to improve the pathways for obtaining biofuels (Nasir et al. 2013; Quiroz-Perez et al. 2019).
Sustainable development of biofuels supply chains from the variety of available feed-
stocks and process routes imply new challenges for Chemical Engineering. In particular,
there are key process design aspects of biofuels production to be improved and intensified
(Nasir et al. 2013; Oh et al. 2018; Raud et al. 2019). They include the collection (harvest-
ing/production or recovery) of the biomass, feedstock pretreatment, biomass transformation
routes, end-products separation and purification, and the corresponding logistic tasks that
are linked to the elements of the supply chain. All these factors impact the economic fea-
sibility of the specific pathway to produce the biofuel. For instance, some authors have
highlighted that the production of 4th generation renewable fuels could imply expensive
Introduction 3
and energy intensive operations thus limiting its current commercialization (Darda et al.
2019). The application of sustainable technologies in each process stage is paramount to
reach the goal of a green and feasible large-scale production of bioenergy. In terms of pro-
cess modeling, there is also the necessity of improving the thermodynamic framework and
conceptual design approaches employed in the biofuels process engineering.
It is clear that biofuels production creates new applications for process system engineer-
ing (PSE) in terms of biomass valorization, green chemistry, thermodynamics, catalysts,
reaction engineering, separation units, process modeling, optimization, design, and con-
trol. Although several developments have been achieved in this direction, there are still
technical limitations and barriers to be overcome with the objective of minimizing costs
and energy requirements of commercial biofuels production facilities utilizing affordable
feedstocks and consequent protection of the environment via energy efficiency and waste
reduction. This book aims to contribute to the development of sustainable production of
renewable biofuels. Specifically, it covers different topics associated with PSE of biofuels
production. The remainder of this chapter is organized as follows: Section 1.2 provides an
overview of relevant issues of PSE associated with biofuels production. Examples of gaps
and current challenges in the production of biofuels are briefly discussed. Finally, Section
1.3 outlines the scope of all the chapters in this book.
1.2 Significance of Process Systems Engineering for Biofuels Production

PSE is devoted to analyzing the elements associated with the creation and operation of
chemical supply chains (Grossmann and Westerberg 2000). This implies the development of
systematic procedures that can be applied in the discovery, design, manufacture and distri-
bution of chemical products starting from the microsystem level until reaching the industrial
scale applications (Grossmann and Westerberg 2000); see Figure 1.1. Undoubtedly, these
Time scale
Month Enterprise
Week Site
Day Plants
Hour
Process units
Minute Single and
multiphase systems
Second Chemical scale
Particle, thin film
ms Small
Molecule
cluster Intermediate
ns
Molecules Large
ps
1 pm 1 nm 1 μm 1 mm 1m 1 km Length scale
Figure 1.1 Conceptual description of a chemical supply chain considering the time, length and chemical
scales. Source: Grossmann and Westerberg 2000. Reproduced with permission of John Wiley & Sons.
PSE elements can be extrapolated to the development of biofuels supply chains, and they
include theoretical, computational and experimental studies.
As stated by Grossmann and Westerberg (2000), research and development in PSE com-
prise the process and product design, process modeling, integration, control and operation,
supporting design methods and numerical tools. The feasible and environmentally friendly
production of biofuels also need advances in these PSE areas (Nasir et al. 2013). The exis-
tence of diverse processing routes for the biomass transformation and the incorporation
of novel technologies with the corresponding discovery of alternative feedstocks are the
main drivers of PSE research in biofuels production. This section provides an overview of
opportunities of PSE areas for the production of renewable fuels. Many of these topics are
analyzed in detail in the other chapters in this book.
1.2.1 Modeling of Physicochemical Properties of Thermodynamic Systems Related

to Biofuels
Thermodynamic modeling of properties of pure components and their mixtures, includ-
ing the prediction of the phase equilibrium behavior, is paramount for the engineering of
biofuels production because it is the basis of process design. Reliable prediction of thermo-
dynamic properties is fundamental to calculate the type and size of different equipment,
profiles of state variables (e.g. concentrations and temperature) of separation units and
energy consumption for separation and purification tasks, and also to identify optimal oper-
ating conditions of reaction systems and other process units. For example, knowledge of
density and viscosity of a given thermodynamic system is relevant for vessel design, piping,
and calculation of mass transfer rates.
As stated, feedstocks for the production of biofuels include biomass by-products (e.g.
forest residues, sugar cane bagasse, cereal straw), urban wastes (e.g. organic compounds
present in industrial and municipal solid and liquid wastes), animal fats, vegetable oils,
insect lipids and dedicated materials as energy crops (Sawangkeaw and Ngamprasertsith
2013; Loman and Ju 2016; Stephen and Periyasamy 2018; Kumar et al. 2020). Conse-
quently, mixtures involved in the process operations to synthetize biofuels are characterized
by the presence of a wide spectrum of organic (e.g. lipids, dyes, aromatic hydrocarbons and
biopolymers) and inorganic compounds (e.g. electrolytes and heavy metals). This complex
composition imposes different challenges in the development and application of suitable
thermodynamic models to predict correctly physicochemical behavior. For instance, the
fatty acid profile of feedstocks can affect the physicochemical properties of biodiesel, and
this profile could change substantially depending on biomass origin (Sawangkeaw and
Ngamprasertsith 2013).
On the other hand, mixtures present in biofuels production usually show non-ideal phase
behavior with complex phase diagrams that could be very sensitive to changes in pres-
sure, temperature and composition. Consequently, thermodynamic calculations required
to predict phase behavior/diagrams of biofuels-based systems usually pose computational
challenges. These calculations involve multivariable and nonlinear problems that are char-
acterized by the potential of multiple solutions due to the complexity of thermodynamic
models. Phase equilibrium calculations must be performed numerous times in the process
simulators for the design, optimization and control of process units. These include Gibbs
free energy minimization to estimate phase compositions, phase stability analysis to verify
Introduction 5
the reliability of solutions obtained for phase equilibrium problems, prediction of bubble
and dew points, critical conditions, azeotropic points, etc.
Reliable determination of parameters of thermodynamic models employed in phase
equilibrium calculations is an additional issue that should be resolved. These adjustable
parameters can be obtained from the regression analysis of experimental data, whose
(un)availability limits the implementation of some thermodynamic models for the
study of biofuels-related systems. Therefore, the application of predictive models and
computer-aided methodologies is necessary to estimate the required physicochemical
properties. Fortunately, there are scientific databanks of experimental physical and
chemical properties of many compounds (Su et al. 2017). However, they usually contain
limited information for the molecules involved in the mixtures associated with biofuels
systems. This issue also highlights the importance of developing a robust thermodynamic
framework for the process design and modeling of the biofuels supply chain.
Computational chemistry approaches, group contribution methods and equation of states
can be utilized to estimate the properties required in biofuels process design at different
modeling scales (i.e. atomic, group, and molecular) (Su et al. 2017). The conventional
thermodynamic models (e.g. cubic equations of state or local composition models) could
fail to predict the physicochemical behavior of biofuels-based systems (Reynel-Avila et al.
2019). Consequently, reliable predictive methods are required to calculate the physical and
chemical properties of pure components and their mixtures in the processing routes of bio-
fuels. Application of artificial intelligence tools such as artificial neural networks and deep
learning can be an interesting option to improve the available models for predicting the
physicochemical performance of biofuels systems (Reynel-Avila et al. 2019). Reliable and
improved numerical methods for solving nonlinear equations and global optimization prob-
lems should be developed to resolve, robustly and efficiently, the mathematical problems
arising in the phase equilibrium modeling of biofuels. In summary, development of robust
and flexible models with improved capabilities, effective solution methods and software
tools for predicting the thermophysical behavior and properties of biofuels-related sys-
tems (from molecular to macroscopic level) is one of the challenges in PSE for biofuels
production.
1.2.2 Intensification of the Biomass Transformation Routes for the Production

of Biofuels
Process intensification is a relevant area of PSE to enhance the performance of biofuels
production routes (Nasir et al. 2013; Quiroz-Perez et al. 2019). Classical schemes for bio-
fuels production imply the operation of process units that work independently without the
integration of mass and energy, where their performance metrics are usually not optimum.
Strategies to intensify the biofuels processing routes have increased substantially allowing
significant reductions in the production cost and environmental impact. Overall, process
intensification principles have been applied in different stages of the pathways for the
transformation of biomasses to biofuels (Nasir et al. 2013; Quiroz-Perez et al. 2019; Wong
et al. 2019).
The diversity of transformation routes for biofuels production has promoted advances
in catalytic and non-catalytic processes, biotechnology, separation and reaction technolo-
gies. For instance, catalyst-based transformation routes are very common to obtain biofuels
(Wong et al. 2019). Transesterification-based processes can be used to convert edible and
non-edible fats and oils into biodiesel, where homogeneous and heterogeneous (acid, base,
or enzymatic) catalysts are employed (Rezania et al. 2019). This processing route may
require a pretreatment stage (e.g. esterification reaction) if the feedstock contains high fatty
acids (Nasir et al. 2013). The need to reduce costs in these processes has led to the synthe-
sis and application of novel catalysts (Trombettoni et al. 2018), the study of novel reaction
media such as supercritical fluids (Deshpande et al. 2010) and the proposal of alternative
reactor technologies (Tabatabaei et al. 2019; Wong et al. 2019).
On the other hand, some authors have concluded that microbial fermentation for obtain-
ing bioalcohols is a simple and promising approach to produce bioenergy (Bhatia et al.
2017). In particular, alcohols with two or more carbon atoms (e.g. ethanol and butanol)
have been considered as interesting alternatives to conventional petroleum-based fuels.
However, fermentation processes utilized in the production of these alcohols have several
disadvantages that limit their large-scale industrial applications. The process intensification
of this route should address the inhibition of competitive pathways that affect the alcohol
productivity due to by-products formed, the genomic adaptation of strains to enhance the
substrate utilization capability to use low cost feedstocks (e.g. lignocellulosic wastes), the
genetic diversification of microbes with improved alcohol producing capabilities to inten-
sify specific metabolic performance for obtaining the desired end-products and to design
synthetic biofuels pathways (Shanmugam et al. 2020). Indeed, advances and developments
in metabolic engineering have contributed to the process intensification of biofuels pro-
duction via the optimization of bioprocess yields and productivities (Shanmugam et al.
2020). Microbial genome engineering can be utilized to maximize the efficiency of fermen-
tation processes via the improvement of the genomic characteristics of biofuels producing
microorganisms to direct the metabolic flux toward the generation of desirable bioproducts
(Shanmugam et al. 2020). Several authors have analyzed and discussed these and other
advances in metabolic engineering and synthetic biology for biofuels production (e.g. Bilal
et al. 2018; Majidian et al. 2018).
Separation units also represent an important area for process intensification in the pro-
duction of biofuels. Separation technologies are utilized in the pretreatment and preprocess-
ing stages of biomass transformation due to the heterogeneous composition of feedstocks
and in the purification of process streams to recover biofuels and their by-products. Both
non-intensive and intensive energy separation methods have been applied in biofuels pro-
duction. Distillation, extraction, adsorption and membrane-based methods are part of the
spectrum of technologies for obtaining renewable fuels (Atadashi et al. 2011; Levario et al.
2012; Abdehagh et al. 2014; Li et al. 2019). The application of intensified non-reactive sep-
arations such as heat-integrated and membrane-based distillation, has been explored in the
production of biofuels (Diaz and Tost 2017; Kumar et al. 2019). Also, intensified schemes
that combine reaction and separation units (e.g. reactive distillation and extraction) (Plesu
et al. 2015; Poddar et al. 2017; Gor et al. 2020), and purification systems assisted with
microwave, ultrasound and supercritical fluids (Patil et al. 2018; Li et al. 2019; Mahmood
et al. 2019) have been reported to produce biofuels.
Separation and purification methods applied in biofuels production show different limita-
tions and advantages in terms of energy consumption and product(s) recovery. For example,
extraction techniques are relevant for biofuels processing that usually require low energy
consumption (Li et al. 2019). Extraction is a key step to carry out the recovery of the
desired bioproducts and to reduce the content of undesired substances in the intermediate
Introduction 7
stream to be processed. Fatty acids, hydrocarbons, lipids and biosolids can be extracted from
extractable feedstocks for biofuels production such as animal fats, energy crops, agricul-
tural residues and microalgae. The selection of the extraction technique is constrained by the
characteristics of the feedstock to be processed and the specific components to be recovered
or concentrated, which impact the separation efficacy and selectivity. Mechanical, physical
and chemical extraction methods have been utilized in the production of different genera-
tion biofuels (Li et al. 2019). Extraction techniques can be intensified via the application
of microwave, ultrasound and supercritical fluids. Also, novel extractive agents such as
ionic liquids and green solvents have been explored to intensify the recovery of the tar-
get compound(s). Li et al. (2019) have analyzed in detail the advantages and limitations
of extraction techniques utilized in biofuels production. These extraction processes may
generate residues that could cause health hazards and environmental pollution, which is an
issue to be resolved as part of PSE challenges.
With respect to energy intensive separation methods, distillation is the primary method in
chemical process industries but its application in the recovery of biofuels depends signifi-
cantly on the characteristics of the streams to be purified. However, conventional distillation
is not an effective approach for the purification of bioalcohols from fermentation broths due
to the occurrence of homogeneous azeotropes (Abdehagh et al. 2014). Therefore, hybrid
and intensified distillation schemes have been applied to recover these and other biofuels.
For example, Nagy et al. (2015) reported that the combination of distillation and pervapo-
ration can decrease the energy demand for downstream separation of fermentation broths.
Several studies have also reported the application of reactive distillation for the production
of biofuels. Reactive distillation allows simultaneous transesterification and separation of
products within the same equipment (Poddar et al. 2017). Several improvements to this
reactive separation scheme to produce different renewable fuels have also been reported
(Gutierrez-Antonio et al. 2018; Gao et al. 2019). See Singh and Rangaiah (2017) for a
review of advances in separation processes for bioethanol recovery and dehyration.
Overall, it is required to develop improved process units that should be flexible and
robust for the transformation of feedstocks with changing physicochemical characteristics
to biofuels. Advanced and less energy-intensity separation techniques are needed to
increase the sustainability of biofuels production. The development of green technologies
for the purification and recovery of biofuels and by-products is considered a relevant
PSE issue. The application of intensification technologies based on supercritical fluids,
microwave, ultrasound, and ionic liquids opens new opportunities for the development
of improved processes for biofuels production. Research on these technologies should
be increased to establish their benefits and limitations for industrial applications. Efforts
should also be focused on the recovery and use of value-added compounds generated
during biomass transformation such as glycerol. These and other shortcomings should be
addressed with the aim of developing cost-effective separation and purification schemes
for the production of biofuels.
1.2.3 Computer-Aided Methodologies for Process Modeling, Design, Optimization,

and Control Including Supply Chain and Life Cycle Analyses
Process design of biofuels production facilities should consider performance metrics
and objectives related to environment, economics, and safety. In particular, current and
anticipated regulations for environmental protection impose additional restrictions to

this design stage. Biofuels process design requires the application of proper models
that accurately represent the characteristics and properties of the systems, units and all
elements involved in the supply chain ranging from the microscopic to macroscopic level
(Figure 1.1). Therefore, development of realistic models to be used in process design is
an important PSE challenge for biofuels production. Note that high level physicochemical
description in the design problem formulation is challenging. For instance, Quiroz-Perez
et al. (2019) have highlighted the importance of computational fluid dynamics for process
design and modeling of equipment involved in biofuels production where transport
phenomena are paramount to ensure correct scale up and industrial operation. Also, kinetic
and thermodynamic data of the reacting systems involved in biomass transformation routes
are fundamental for reliable design of reactors including fermenters.
Processing routes for biofuels production can be optimized via the formulation of design
problems with one or more objectives to be minimized or maximized simultaneously.
Indeed, multi-objective optimization (MOO) has found numerous applications in chemical
engineering and related areas (Rangaiah and Bonilla-Petriciolet 2013; Rangaiah et al.
2015; Madoumier et al. 2019). Optimization can be employed to improve the performance
of specific process units and the entire processing route for producing biofuels. Biofuels
process optimization is not an easy task and robust numerical methods are required to solve
the design problems, which are usually multivariate, nonlinear and with equality/inequality
constraints. Deterministic and stochastic optimizers have been applied to solve design
problems in the biofuels production. In particular, stochastic optimizers (metaheuristics)
have shown several advantages for solving both global optimization and MOO problems of
biofuels production due to their easy implementation, computational efficiency and ability
to handle both discrete and continuous design variables. Optimization has been used for
the design of intensified separation sequences for biofuels purification (Sanchez-Ramirez
et al. 2019; Gor et al. 2020), for the improvement of processing routes to obtain biofuels
(Woinaroschy 2014), for the integrated design of biorefineries to produce biodiesel from
different feedstocks (Prieto et al. 2017), to identify processing paths for obtaining biofuels
from different feedstocks (Eason and Cremaschi 2014), and for biodiesel plant design
(Patle et al. 2014a; Alvaraes et al. 2019).
Biofuels production facilities comprise a large set of operating variables that should be
manipulated and regulated. Therefore, process controllability is an important issue for the
implementation, operation and safety of biofuel production. The control problem of a com-
plete biofuels production process is large with nonlinear functions of states, many inputs
and outputs, and a reduced number of degrees of freedom (Bildea and Kiss 2011; Prunescu
et al. 2017). Consequently, nonlinear control concepts and plantwide control are required to
achieve flexible and stable operation of process units in biofuels production. For example,
plantwide control has been studied for a complete biodiesel plant (Patle et al. 2014b).
Life cycle analysis (LCA) is desirable for comprehensive assessment of the sustainability
of biofuels processes in terms of environmental, social, energetic and economic indicators
(Collotta et al. 2019). Several authors have reported LCA of the production of renewable
fuels using different levels of details, methodologies, analytical boundaries, and impact
metrics (e.g. Mu et al. 2017; Liu et al. 2018). However, it has been pointed out that the stan-
dardization of methodologies utilized for LCA of biofuels, including life cycle inventory
data, is a relevant issue to be addressed for performing reliable comparison and supporting
Introduction 9
the decision-making process to identify the best options for biofuels production (Mayer
et al. 2020).
Finally, biofuels supply chains include all the activities related to the transformation of
biomasses into renewable fuels and their delivery to the end-users (An et al. 2011; Awudu
and Zhang 2012). The biofuels supply chain is affected by several uncertainties in terms
of prices, demand and supply of feedstocks and end-products, transportation and storage
issues, performance of processing facilities, among other factors (Awudu and Zhang 2012).
Consequently, the design of a reliable and sustainable biofuels supply chain requires the
application of the latest computer-aided methodologies to optimize the operational, tactical
and strategic decisions.
In summary, PSE contributions and developments are fundamental to consolidate, opti-
mize and operate the biofuels supply chains to achieve the economic, environmental and
social benefits of this type of renewable energy.
1.3 Overview of this Book

After this chapter, this book contains 12 chapters that describe and analyze different applica-
tions of PSE for biofuels production. Chapters 2–13 are briefly summarized in this section.
Chapter 2 provides an overview of different biomasses that can be utilized for biofuels
production. It highlights the relevance of feedstock composition for biofuels production.
Biomasses analyzed in this chapter include spent coffee grounds, different lignocellulosic
materials, residues of oil production from palm, olive, coconut, avocado and argan, residues
from crops such as citrus and grapes, and waste oil and waste cooking oil. This chapter ends
stating the importance of developing new methods and technologies to exploit the variety
of available feedstocks for producing biofuels.
In Chapter 3, analysis and discussion of PSE contributions for the process design of
biorefineries and biomass-based infrastructure are presented. This chapter describes meth-
ods for the design of process units and approaches for process synthesis. The product design
problem for biomass processing, supply chain modeling and the importance of multiscale
analysis are also discussed.
The challenges of thermodynamic properties and phase equilibrium calculations in bio-
fuels process design are covered in Chapter 4. Elements of the thermodynamic model-
ing framework for the prediction of properties required for process design of biofuels are
described. The formulation of phase equilibrium problems and a survey of available thermo-
dynamic models for phase equilibrium calculations are presented. A brief analysis of prop-
erty databanks for biofuels process design and the impact of uncertainties of thermophysical
properties are also provided in this chapter. Finally, some methods for the prediction of
thermodynamic properties of compounds involved in biofuels production are described.
Chapters 5 reports pretreatment methods and processing routes to transform waste oil
into biodiesel. Capabilities and limitations of homogeneous and heterogeneous catalysis,
enzymatic-, ionic liquid- and hydrated salts-based conversions for processing waste oils
are discussed. The authors of this chapter have highlighted the technical limitations and
challenges to intensify biodiesel production from waste oil.
Biojet fuel production from wastes and residues is reviewed in Chapter 6. This chapter
discusses the importance of biofuels development for the aviation sector. It contains the
state of the art in the processing of triglyceride-containing wastes, lignocellulosic materials,

sugar and starchy residues for the production of biojet fuel. The authors of this chapter have
analyzed the challenges and future trends to potentiate this renewable fuel for the aviation
industry.
Computer-aided design is important to develop new processes for the production of
biofuels. Therefore, Chapter 7 focuses on the development of a simulation platform for
biological models associated with biofuels systems. The modeling approach involves an
optimization problem subject to specific constraints. Two examples are reported to show
the application of this modeling approach. Results show that this approach can be used to
assist the industrial production of biofuels via mutated strains.
Different aspects of PSE of biodiesel production via enzyme-catalyzed routes are ana-
lyzed in Chapter 8. A comparison of the biodiesel production routes with chemical and
enzymatic catalysts is performed. The authors have discussed the optimal reaction condi-
tions and the kinetic modeling in biodiesel production routes catalyzed by liquid enzymes.
Details of process simulation and economic evaluation of this type of transformation route,
including the reuse of the enzymes, are also included in this chapter.
Chapter 9 deals with simulation and design of process scenarios for biodiesel production.
In particular, this chapter describes the application of the Aspen Plus® simulator to model
the biodiesel process. Examples are described for the calculation of thermodynamic prop-
erties of both pure components and mixtures, required for process design. Also, the authors
have discussed some aspects of utilization of Aspen Plus to model reactions involved in
biodiesel production. Case studies related to the process design of esterification and trans-
esterification reactions with different reactor models are described. Finally, use of Aspen
Plus for energy and economic analyses is illustrated. This chapter provides a simple and
handy guide for students and practitioners in the use of Aspen Plus for biofuels process
design.
Chapter 10 also describes the modeling and simulation of a continuous biodiesel pro-
cess from microalgae using Aspen Plus. For this, process parameters and reaction kinetic
data were based on reported experimental results. A sensitivity analysis was performed to
analyze the impact of some design variables of process units. The sizing and cost analysis
of the equipment utilized in the biodiesel process simulation were carried out. The authors
compared the performance of this biodiesel process from microalgae with the results for a
biodiesel process using waste cooking oil. Based on this, some research topics to reduce
the cost of biodiesel production from wet microalgae are suggested.
A state of the art of thermochemical methods for the production of renewable fuels
is given in Chapter 11. Thermochemical methods that are utilized to obtain solid, liquid
and gaseous biofuels are described in this chapter. First, a simple classification of ther-
mochemical methods is provided. Combustion, gasification, liquefaction, pyrolysis, and
carbonization are analyzed. Advantages, limitations, energy requirements and equipment
used in these thermochemical methods are also covered in this chapter.
A perspective of the present and future of biofuels is presented in Chapter 12. The
importance, implications and advantages of utilizing biomass to produce renewable energy
are analyzed. Characteristics of some biofuels feedstocks and their processing routes are
provided. This chapter includes a detailed discussion of bioethanol, biodiesel, biobutanol,
biojet fuel, and biogas. It concludes that biofuels production from some specific feedstocks
will be commercially attractive in the next decade.
Introduction 11
Finally, Chapter 13 deals with the design of intensified purification options to produce
methyl ethyl ketone, which has been suggested as a biofuel that can be produced by the fer-
mentation route. Purification of mixtures that contain this biofuel is challenging due to the
presence of azeotropes. Hence, this chapter analyzes some intensified schemes to improve
methyl ethyl ketone purification. Separation schemes based on distillation and liquid–liquid
extraction were designed via the MOO approach considering economic, environmental,
controllability and safety indexes. Results show that the intensified process requires lower
energy compared with the separation scheme based on distillation alone.
In short, the contents of this book expand and cover developments and contributions of
PSE for biofuels production. Students of Chemical Engineering, Environmental Engineer-
ing, Energy Engineering and related areas will find the chapters useful in their studies on
biofuels. The editors and authors of this book hope that its contents will contribute to further
research and development of PSE for biofuels production in both academia and industrial
practice. As stated, biofuels are at the forefront of new energy solutions to the environmental
and safety problems related to the use of petroleum-based fuels. Consequently, consoli-
dation of biofuels production and supply chains are important to support the sustainable
human development of future generations.
References
Abdehagh, N., Tezel, F.H., and Thibault, J. (2014). Separation techniques in butanol production: challenges
and developments. Biomass and Bioenergy 60: 222–246.
Alvaraes, A.O., Prata, D.M., and Santos, L.S. (2019). Simulation and optimization of a continuous biodiesel
plant using nonlinear programming. Energy 189: 116305.
An, H., Wilhelm, W.E., and Searcy, S.W. (2011). Biofuel and petroleum-based fuel supply chain research:
a literature review. Biomass and Bioenergy 35: 3763–3774.
Atadashi, I.M., Aroua, M.K., and Aziz, A.A. (2011). Biodiesel separation and purification: a review. Renew-
able Energy 36: 437–443.
Awudu, I. and Zhang, J. (2012). Uncertainties and sustainability concepts in biofuel supply chain manage-
ment: a review. Renewable and Sustainable Energy Reviews 16: 1359–1368.
Bhatia, S.K., Kim, S.H., Yoon, J.J., and Yang, Y.H. (2017). Current status and strategies for second genera-
tion biofuel production using microbial systems. Energy Conversion and Management 148: 1142–1156.
Bilal, M., Iqbal, H.M.N., Hu, H. et al. (2018). Metabolic engineering and enzyme-mediated processing:
a biotechnological venture towards biofuel production – a review. Renewable and Sustainable Energy
Reviews 82: 436–447.
Bildea, C.S. and Kiss, A.A. (2011). Dynamics and control of a biodiesel process by reactive absorption.
Chemical Engineering Research and Design 89: 187–196.
Collotta, M., Champagne, P., Tomasoni, G. et al. (2019). Critical indicators of sustainability for biofuels: an
analysis through a life cycle sustainability assessment perspective. Renewable and Sustainable Energy
Reviews 115: 109358.
Darda, S., Papalas, T., and Zabaniotou, A. (2019). Biofuels journey in Europe: currently the way to low
carbon economy sustainability is still a challenge. Journal of Cleaner Production 208: 575–588.
Deshpande, A., Anitescu, G., Rice, P.A., and Tavlarides, L.L. (2010). Supercritical biodiesel produc-
tion and power cogeneration: technical and economic feasibilities. Bioresource Technology 101:
1834–1843.
Diaz, V.H.G. and Tost, G.O. (2017). Energy efficiency of a new distillation process for isopropanol, butanol
and ethanol (IBE) dehydration. Chemical Engineering and Processing: Process Intensification 112:
56–61.
Eason, J.P. and Cremaschi, S. (2014). A multi-objective superstructure optimization approach to

biofeedstocks-to-biofuels systems design. Biomass and Bioenergy 63: 64–75.
Gao, X., Tu, S., Li, T., and Li, H. (2019). Feasibility evaluation of reactive distillation process for the
production of fuel ethanol from methyl acetate hydrotreating. Chemical Engineering and Processing:
Process Intensification 139: 34–43.
Gor, N.K., Mali, N.A., and Joshi, S.S. (2020). Intensified reactive distillation configurations for production
of dimethyl ether. Chemical Engineering and Processing: Process Intensification 149: 107824.
Grossmann, I.E. and Westerberg, A.W. (2000). Research challenges in process systems engineering. AIChE
Journal 46: 1700–1703.
Gutierrez-Antonio, C., Gomez-Castro, F.I., de Lira-Flores, J.A., and Hernandez, S. (2017). A review on the
production processes of renewable jet fuel. Renewable and Sustainable Energy Reviews 79: 709–729.
Gutierrez-Antonio, C., Ornelas, M.L.S., Gomez-Castro, F.I., and Hernandez, S. (2018). Intensification of
the hydrotreating to produce renewable aviation fuel through reactive distillation. Chemical Engineering
and Processing: Process Intensification 124: 122–130.
Hassan, S.N., Sani, Y.M., Abdul Aziz, A.R. et al. (2015). Biogasoline: an out-of-the-box solution to the
food-for-fuel and land-use competitions. Energy Conversion and Management 89: 349–367.
Kumar, M., Sun, Y., Rathour, R. et al. (2020). Algae as potential feedstock for the production of biofuels
and value-added products: opportunities and challenges. Science of the Total Environment 716: 137116.
Kumar, R., Ghosh, A.K., and Pal, P. (2019). Fermentative ethanol production from madhuca indica flow-
ers using immobilized yeast cells coupled with solar driven direct contact membrane distillation with
commercial hydrophobic membranes. Energy Conversion and Management 181: 593–607.
Levario, T.J., Dai, M., Yuan, W. et al. (2012). Rapid adsorption of alcohol biofuels by high surface area
mesoporous carbons. Microporous and Mesoporous Materials 148: 107–114.
Li, P., Sakuragi, K., and Makino, H. (2019). Extraction techniques in sustainable biofuel production: a
concise review. Fuel Processing Technology 193: 295–303.
Liu, H., Huang, Y., Yuan, H. et al. (2018). Life cycle assessment of biofuels in China: status and challenges.
Renewable and Sustainable Energy Reviews 97: 301–322.
Loman, A.A. and Ju, L.K. (2016). Soybean carbohydrate as fermentation feedstock for production of bio-
fuels and value-added chemicals. Process Biochemistry 51: 1046–1057.
Madoumier, M., Trystram, G., Sebastian, P., and Collignan, A. (2019). Towards a holistic approach for
multi-objective optimization of food processes: a critical review. Trends in Food Science & Technology
86: 1–15.
Mahmood, H., Moniruzzaman, M., Iqbal, T., and Khan, M.J. (2019). Recent advances in the pretreatment
of lignocellulosic biomass for biofuels and value-added products. Current Opinion in Green and Sus-
tainable Chemistry 20: 18–24.
Majidian, P., Tabatabaei, M., Zeinolabedini, M. et al. (2018). Metabolic engineering of microorganisms for
biofuel production. Renewable and Sustainable Energy Reviews 82: 3863–3885.
Mayer, F.D., Brondani, M., Carillo, M.C.V. et al. (2020). Revisiting energy efficiency, renewability and
sustainability indicators in biofuels life cycle: analysis and standardization proposal. Journal of Cleaner
Production 252: 119850.
Mu, D., Ruan, R., Addy, M. et al. (2017). Life cycle assessment and nutrient analysis of various processing
pathways in algal biofuel production. Bioresource Technology 230: 33–42.
Nagy, E., Mizsey, P., Hancsok, J. et al. (2015). Analysis of energy saving by combination of distillation and
pervaporation for biofuel production. Chemical Engineering and Processing: Process Intensification 98:
86–94.
Nasir, N.F., Daud, W.R.W., Kamarudin, S.K., and Yaakob, Z. (2013). Process system engineering in
biodiesel production: a review. Renewable and Sustainable Energy Reviews 22: 631–639.
Oh, Y.K., Hwang, K.R., Kim, C. et al. (2018). Recent developments and key barriers to advanced biofuels:
a short review. Bioresource Technology 257: 320–333.
Introduction 13
Patil, P.D., Dandamudi, K.P.R., Wang, J. et al. (2018). Extraction of bio-oils from algae with supercritical
carbon dioxide and co-solvents. Journal of Supercritical Fluids 135: 60–68.
Patle, D.S., Sharma, S., Ahmad, Z., and Rangaiah, G.P. (2014a). Multi-objective optimization of two alkali
catalyzed processes for biodiesel from waste cooking oil. Energy Conversion and Management 85:
361–372.
Patle, D.S., Ahmad, Z., and Rangaiah, G.P. (2014b). Plantwide control of biodiesel production from waste
cooking oil using integrated framework of simulation and heuristics. Industrial and Engineering Chem-
istry Research 53: 14408–14418.
Plesu, V., Puigcasas, J.S., Surroca, G.B. et al. (2015). Process intensification in biodiesel production with
energy reduction by pinch analysis. Energy 79: 273–287.
Poddar, T., Jagannath, A., and Almansoori, A. (2017). Use of reactive distillation in biodiesel production:
a simulation-based comparison of energy requirements and profitability indicators. Applied Energy 185:
985–997.
Prieto, C.V.G., Ramos, F.D., Estrada, V. et al. (2017). Optimization of an integrated algae-based biorefinery
for the production of biodiesel, astaxanthin and PHB. Energy 139: 1159–1172.
Prunescu, R.M., Blanke, M., Jakobsen, J.G., and Sin, G. (2017). Model-based plantwide optimization of
large scale lignocellulosis bioetanol plants. Biochemical Engineering Journal 124: 13–25.
Quiroz-Perez, E., Gutierrez-Antonio, C., and Vázquez-Roman, R. (2019). Modelling of production pro-
cesses for liquid biofuels through CFD: a review of conventional and intensified technologies. Chemical
Engineering and Processing: Process Intensification 143: 107629.
Rangaiah, G.P. and Bonilla-Petriciolet, A. (eds.) (2013). Multi-Objective Optimization in Chemical Engi-
neering: Developments and Applications. Wiley.
Rangaiah, G.P., Sharma, S., and Sreepathi, B.K. (2015). Multi-objective optimization for the design and
operation of energy efficient chemical processes and power generation. Current Opinion in Chemical
Engineering 10: 49–62.
Raud, M., Kikas, T., Sippula, O., and Shurpali, N.J. (2019). Potentials and challenges in lignocellulosic
biofuel production technology. Renewable and Sustainable Energy Reviews 111: 44–56.
Reynel-Avila, H.E., Bonilla-Petriciolet, A., and Tapia-Picazo, J.C. (2019). An artificial neural
network-based NRTL model for simulating liquid-liquid equilibria of systems present in biofuels
production. Fluid Phase Equilibria 483: 153–164.
Rezania, S., Oryani, B., Park, J. et al. (2019). Review on transesterification of non-edible sources for
biodiesel production with a focus on economic aspects, fuel properties and by-product applications.
Energy Conversion and Management 201: 112155.
Sanchez-Ramirez, E., Quiroz-Ramirez, J.J., Hernandez, S. et al. (2019). Synthesis, design and optimization
of alternatives to purify 2,2-butanediol considering economic environmental and safety issues. Sustain-
able Production Consumption 17: 282–295.
Sawangkeaw, R. and Ngamprasertsith, S. (2013). A review of lipid-based biomasses as feedstocks for bio-
fuels production. Renewable and Sustainable Energy Reviews 25: 97–108.
Shanmugam, S., Ngo, H.H., and Wu, Y.R. (2020). Advanced CRISPR/Cas-based genome editing tools for
microbial biofuels production: a review. Renewable Energy 149: 1107–1119.
Singh, A. and Rangaiah, G.P. (2017). Review of Technological Advances in Bioethanol Recovery and
Dehyration. Industrial and Engineering Chemistry Research 56: 5147–5163.
Stankiewicz, A.I. and Moulijn, J.A. (2000). Process intensification: transforming chemical engineering.
Chemical Engineering Progress 96: 22–33.
Stephen, J.L. and Periyasamy, B. (2018). Innovative developments in biofuels production from organic
waste materials: a review. Fuel 214: 623–633.
Su, W., Zhao, L., and Deng, S. (2017). Group contribution methods in thermodynamic cycles: physical
properties of pure working fluids. Renewable and Sustainable Energy Reviews 79: 984–1001.
Tabatabaei, M., Aghbashlo, M., Dehhaghi, M. et al. (2019). Reactor technologies for biodiesel production
and processing: a review. Progress in Energy and Combustion Science 74: 239–303.
Tian, Y., Demirel, S.E., Hasan, M.M.F., and Pistikopoulos, E.N. (2018). An overview of process systems
engineering approaches for process intensification: state of the art. Chemical Engineering and Process-
ing: Process Intensification 133: 160–210.
Trombettoni, V., Lanari, D., Prinsen, P. et al. (2018). Recent advances in sulfonated resin catalysts for
efficient biodiesel and bio-derived additives production. Progress in Energy and Combustion Science 65:
136–162.
Wei, H., Liu, W., Chen, X. et al. (2019). Renewable bio-jet fuel production for aviation: a review. Fuel 254:
115599.
Woinaroschy, A. (2014). Multiobjective optimal design for biodiesel sustainable production. Fuel 135:
393–405.
Wong, K.Y., Ng, J.H., Chong, C.T. et al. (2019). Biodiesel process intensification through catalytic enhance-
ment and emerging reactor design: a critical review. Renewable and Sustainable Energy Reviews 116:
109399.
2
Waste Biomass Suitable as
Feedstock for Biofuels Production
Maria Papadaki
Department of Environmental Engineering, University of Patras, Agrinio, 30100, Greece
2.1 Introduction
2.1.1 The Need for Biofuels
Babu (2008) defines biomass as a term used to describe all Earth’s living matter. It is a
general term for material derived from growing plants or from animal manure (which is
effectively a processed form of plant material), while, according to Jessup (2009), biofuels
are solid, liquid, or gaseous energy sources derived from renewable biomass sources. On
the other hand, in article 2 of the European Community Directive “On the promotion of the
use of biofuels” specific definitions of a narrower spectrum are given. As such, the term
“biomass” is used to express the biodegradable fraction of products, waste and residues
from agriculture (including vegetal and animal substances), forestry and related indus-
tries, as well as the biodegradable fraction of industrial and municipal waste. The term
“biofuels” is exclusively referred to liquid or gaseous fuel for transport, i.e. the directive
focuses in fuels which can partially replace fossil-origin fuels employed in transport. It
describes specific characteristics of “bioethanol,” “biodiesel,” “biogas,” “biomethanol,”
“biodimethylether,” “bio-ethyl tert-butyl ether,” “bio- methyl tert-butyl ether,” “synthetic
biofuels,” “biohydrogen,” “pure vegetable oil” which are the referred biofuels, which natu-
rally originate from processed biomass. In this work, the broader definitions are preferred,
although a great deal of the chapter focuses on biomass which can provide liquid and gas
biofuels.
Process Systems Engineering for Biofuels Development, First Edition.

Edited by Adrián Bonilla-Petriciolet and Gade Pandu Rangaiah.
© 2020 John Wiley & Sons Ltd. Published 2020 by John Wiley & Sons Ltd.
Biomass has always been used for the production of energy. Chemicals and pharma-
ceutical products have been obtained from biomass; biomass has been burnt to produce
energy since fire was harnessed. Since the energy crisis of 1973, considerable interest has
developed in biomass use toward meeting the energy needs of the world. Furthermore, the
interest in valorization of biomass was awakened as the awareness of the finite nature of
fossil liquid and gaseous hydrocarbons and their ultimate depletion rose. There was much
argument over when this would occur (Goldstein 2018). However, in the mind of society
the search for alternative energy sources had begun.
A drop in oil prices in the 1990s kept bioenergy markets apart from the production. But
the reliance on fuel supplies from a few major producers and the need to reduce greenhouse
emissions imposed the search for renewable sources of energy; valorization of biomass was
a good option. Special attention was given to the replacement of transport fuels as their
numbers were steadily rising (Karp and Halford 2010). The European Union in particular
in 2008 decided that by 2020, one fifth of the totally consumed energy should be obtained
from a renewable energy reservoir. Great weight was also given to the energy consumed
for transportation. As such, biofuels were expected and resolved to comprise at least 10%
of the energy used in that sector by the end of the second decade of the twenty-first century
(Rechberger and Lötjönen 2009). Renewable forests and field crops appeared to be attrac-
tive and suitable sources of biomass in processes aiming at generating biofuels. Moreover,
it was expected that existing technology could function efficiently and that it was a feasible
solution toward meeting set targets of gradual fossil fuel replacement. In fact, by the end
of the first decade of the twenty-first century a high production of biofuels was reached
in both North and South America. Brazil, Argentina, and the United States produced and
consumed large amounts of bioethanol. A very high percentage of liquid biofuels mainly
in the form of bioethanol was also employed in Australia, China, and Canada. Europe was
predominantly producing and utilizing biodiesel (Azadia et al. 2017).
Appropriate for biofuel production biomass includes in principle, food-crops containing
sugars and starch or crops which have high oil content; those can be converted to appropri-
ate fuels via a sequence of transformation and reaction paths. Biomass of lignocellulosic
content is also a very good candidate. It can be either obtained as the side or waste product
of other processes, such as agricultural and forestry residues. It can also be obtained via pur-
posefully cultivated plants in the form of the so-called energy crops. Additional sources for
biofuel production are: used and waste oils, other organic wastes, algae (micro- or macroal-
gae, encountered or grown in open or pond waters or in photobioreactors) (Stafford et al.
2017). Every year, the plants on Earth produce and store up to four times the energy needed
by humanity per annum (Guo et al. 2015). As such, shrewd, systems-approach planning
for the valorization of the available biomass can substantially reduce our dependency on
fossil fuels. However, to reach such a goal, a number of parameters have to be accounted
for prior to investment in new processes. The aim of producing replacement fuels has to
be harmonically enlaced with objectives such as CO2 reduction, independence from a few
energy providers in the world, that fossil fuels replacement does not impact on food produc-
tion and availability, that deforestation is not a consequence, etc. In other words, the urge
for biofuel production will not be shifting the problems associated with energy elsewhere,
thus forming alternative types and kind of dependencies. Moreover, new, fit-for-purpose
technologies have to be developed and the industrial size production of large quantities
of desired commodities may have to be questioned and probably partially shifted or be
Waste Biomass Suitable as Feedstock for Biofuels Production 17
replaced by smaller, specialized-goods production. Alternative methods of production that

are mobile, transformable, or of extendable or shrinkable capacities may need to be invented
and evolve. Alternative products of a functionality similar to the one offered by existing
commodities, or entities with completely new properties and potential uses may also arise
as side or by-products of the alternative energy production processes.
The selection of good or adequately suitable feedstocks for biofuels production is a ques-
tion with multiple answers. Many of the answers which have been given so far have created
more important questions. Much progress is being made however, thanks to the substan-
tial research already conducted and which is continuously expanding. In the search of such
feedstocks, one has to wind through a multi-stage and multi-scale labyrinthine pathway
in order to first identify the primary qualities required in the feedstock, to subsequently
devise the processes which have the potential to provide expected outputs and to finally
implement a multi-objective optimization process in order to guarantee the viability of the
venture. There are multiple issues which have to be addressed and the primary ones lie
in the definition of the problem which is to be solved. The top-to-bottom approach is tra-
ditionally implemented by the chemical engineers during the conceptual process design.
The problem is relatively static, with well defined raw materials and desired products; the
engineer searches for the best route to take from the starting to the end point. Biomass
valorization and the production of biofuels from biomass form an unprecedented opportu-
nity for the implementation and development of the-top-to-bottom, bottom-to-top coupled
method, described in detail by Pham and El-Halwagi (2012). The method can be also
coupled with the atomic targeting and design (El-Halwagi 2017). Furthermore, in their
book Sengupta and Pike (2012) present how different chemicals including biofuels can
be obtained from waste biomass. They focus on processes which can contribute toward a
sustainable economy. They present the advances of chemistry and technologies which can
be used toward biomass valorization and how non-renewable feedstocks can be replaced
by renewable ones.
Furthermore, given the dynamics and the volatility of the market in the globalized world
an embedded flexibility in the kind of the products, the methods of production, and the
capacity may counterbalance any costs which may affect the economics and the viability of
the process. Thus, space should be sought for versatile designs to replace traditional rigid
requirements where stability of the selected feedstock and product prices are the key factors
governing the process economics.
2.1.2 Problem Definition

Until the end of the first decade of the twenty-first century the raw materials for biofuel pro-
duction were carefully selected and they were obtained through cultivations dedicated to
that very purpose. Associated with this objective, agricultural cultivation involved starchy,
sugary and oily plants which would otherwise have been used for the production of food.
Moreover, the land employed for their growth would have normally been used for the pro-
duction of vegetables for feeding people. This had its impact on agricultural products, rais-
ing their prices, with tropical deforestation due to the expansion of food and non-food crop
cultivation in those areas. Thus, the apparent solution of the energy problem was causing a
number of new problems. As such, the net result was not moving the situation forward; the
energy availability problem was just transformed to another entity. However, the technolo-
gies which have been developed, the research which has been conducted, and the wisdom
which has been acquired can be implemented in the valorization of biomass of a differ-
ent origin, such as waste and residual biomass and perennial grasses. Such an application
will provide additional economic and environmental benefits. Naturally, the exploitation of
these alternative sources of biomass will not be as straightforward as the collection of the
waste biomass; the variability of its composition, its potential degradation before treatment,
and discontinuity in availability pose different technological challenges. However, sustain-
ability is a parameter which always has to be taken into consideration. Cyclic economy is
also gaining ground in the engineering thinking and objectives for future development. As
such, the value of bioenergy, instead of being measured merely in terms of the quantity of
the replaced fossil fuels, should be holistically assessed and the impact that it has on the
food production, on the forests and the potential deforestation, on the spent water resources
and their pollution, on its effects on the wildlife, the soils, and society should be “measured”
and accounted for (Union of Concerned Scientists 2012).
Furthermore, the initial approach of employing corn, and other crops rich in sugars and
starch, traditionally used to cover needs of human and animal food, is proven incapable
of reaching the required needs for bioethanol as transport fuel (Sarkar et al. 2012). On the
other hand, there is a great quantity of organic wastes produced and accumulated via human
activities (city, kitchen, agricultural, animal-farm wastes, wastes of lignocellulosic origin
such as forest residues or residual ligocellulosic mass from other processes) which can be
exploited for the production of biofuels via a number of appropriately designed processes
(Stephen and Periyasamy 2018). Amongst those, excellent quality lignocellulosic waste
biomass can be accumulated from the residuals of crops production (wheat, corn, barley,
rye, oats, and others), from a number of different agricultural activities as well as from the
residual biomass of food industry branches which employ processing of freshly collected
fruits and vegetables, such as the juice industry for instance. The option of plant-origin
waste biomass also consists of an environmentally friendlier way of disposal (Rivas-Cantu
et al. 2013).
2.1.3 The Biomass Pool

The waste biomass which can be used for biofuels production ranges from anything which
can be burnt, producing thermal energy as a solid fuel, to more sophisticated specialized
waste, which can provide high efficiency and high quality liquid biofuels. Waste biomass
which can be used for the production of biofuels can be:
1. Waste biomass which is generated as a by-product or residual product following agricul-
tural activities for the production of food. Typical examples are branches of fruit trees
after pruning, fruit tree leaves, husks of legumes and their stems and leaves, wild vege-
tation trimmings, corn residues, like rice, wheat, barley, oat, rye, millet straws, sorghum
stalks, cassava peels and stalks, yam straws, and nut shells.
2. Forest material which involves branches and leaves of forest trees, willow, poplar, bam-
boo, canes, sawdusts, firewood, and woodchips.
3. Uncontrolled growth wild type vegetation like perennial grasses and shrubs such as
switchgrass, miscanthus, jatropha, algae, micro- and macroalgae and vascular land
plants.
4. Waste energy cane. Energy cane refers to high biomass sugarcane.
5. Natural cosmetics industries waste biomass like seeds, roots, stems and peels of fruits
and vegetables.
6. Food industry waste: remains of plant or animal origin, fish remains, bones, skins, fer-
mentations waste biomass, frying oils and other fats, corn cobs, coffee and other bever-
ages of plant origin waste biomass, sugarcane and sugar beet waste, kernels and shells
of nuts, etc.
7. Waste from human activities, city and general waste, plastics, paper, waste food, waste
tires, greenhouses plastic sheets, and crop protection plastic nets.
8. Other organic waste like animal and poultry manure, and energy industry waste of oil
or lignocellulosic origin (see Figure 2.1).
Such biomass feedstocks can be used to produce biofuels via a number of treatment
methods. The methods of treatment and their value as biofuel feedstocks depends on their
chemical composition and on their content in cellulosic compounds, sugars and carbo-
hydrates and their content in oils. However, a great variety of those also contain small
quantities of compounds which have valuable properties as natural medicinal, food or cos-
metic agents. Furthermore, their potential use as biofuel feedstock often solves the problem
of their disposal as a waste.
There are different ways that this biomass can be treated so as to provide valuable prod-
ucts. The main methods of biofuel production employ processes such as anaerobic fer-
mentation, pyrolysis and co-pyrolysis, gasification, transesterification, fermentation, acid
or base hydrolysis, solvent extraction supercritical or not, simple mechanical processes of
grinding and pelletizing, simple thermal treatment such as drying, direct biomass combus-
tion, or combinations of the above.
Figure 2.1 Sugar canes. Source: Truncated photo from https://www.pexels.com/search/agricultural

%20waste.
The chemical composition of the biomass is a very important factor when seeking the
most appropriate methods of treatment which could potentially be employed. However, the
uniformity of biomass in terms of composition, the variation of its availability during the
year, the potential need of collection, transportation and storage are factors which define
the kind of process which will make its exploitation economically viable and the quantity
and quality of the products which can be obtained. As such, before selecting a specific type
of biomass, the following type of questions have to be answered.
What secondary biomass is already available? Is the selected biomass accessible? In
what quantities? What are their qualities (characteristics)? How is its distribution through
time? What is its spatial distribution? How long can it be stored for before degrading or
suffering an alteration of its composition? In which form should it be stored? Does it need
to be transported? How easy will that be? Can transport fuels be obtained? Can they be
used locally? Is their quality better or worse than that of the fossil fuels (i.e. what is their
nitrogen and/or sulfur content?).
Furthermore, the importance of its valorization as a biofuel has to be assessed in addi-
tional terms which involve safety, environment, and society. For example, does its use
for biofuel production solve any other problems? Does it result in a substantial reduc-
tion of the environmental impact that it would otherwise provoke as waste? Does it con-
tribute toward local or national energy independence? Does it reduce the energy footprint
by reducing transportation of fossil fuels in the area? Does it produce a safer alternative
to employed energy sources? Does it contribute to the economic development of the area
without shifting problems to other places in the world? Does it help the preservation of
biodiversity?
In a preliminary evaluation of the biomass valorization, the geography and the pop-
ulation of the area of the industrial process are of crucial importance for this type of
enterprise and the collection and transportation of residual biomass can constitute an
important expense while the long term storage of biomass is of crucial importance for
its quality. As such, mobile units of treatment or multiple establishments of small units
versus one large facility may be worth considering. Moreover, the potential of extraction
of high added value compounds prior to biorefining may substantially increase the
financial potential of the process. This often implies that the biomass under question has
already been well and reliably characterized. In the following paragraphs a number of
promising feedstocks is presented. Amongst the huge multitude of potential feedstocks
a few selected biomasses are discussed. Their primary common characteristic is their
relative abundance and a substantial amount of completed research on their characteristics.
The reason for the selection of each specific biomass is explained in the relevant sections
(Figure 2.2).
2.2 Kinds of Feedstock

A number of potential feedstocks are presented in the following sections. Each feedstock
is accompanied by a description which intends to answer as many of the above questions
as possible.
Figure 2.2 Equisetum. A plant with important medicinal and pesticide properties, abundantly encoun-
tered in wet soils. Potential biofuels precursor following extraction of added value compounds.
2.2.1 Spent Coffee Grounds

According to the European Coffee Federation (ECF 2016), a few billions of coffee cups are
consumed daily all over the world thus making it the most extensively preferred beverage
worldwide: the USA consumed about one and a half million tons of coffee each year for the
period 2011–2013. Mexico consumes two hundred thousand tons, Brazil over one million
tons, while the EU consumes about two and a half million tons of coffee; however, it imports
around three million tons, part of which is re-exported. The amount of coffee produced in
2015 was approximately nine million tons; from each kilogram of coffee, 0.91 kg of solid
waste is produced, thus the importance of a further valorization of this residue becomes
obvious. As Murthy and Naidu (2012) confirm, coffee is a very popular drink and as such
its trade is extensive.
In a comprehensive review, Campos-Vega et al. (2015) report a detailed catalog of com-
pounds which can be exploited by spent coffee grounds, as the cited research articles in
the review suggest. In the mentioned review, it is proposed to use spent coffee grounds in
order to extract several added value products. More specifically they state that the resid-
ual mass after the initial coffee extraction contains numerous organics like different kinds
of polysaccharides and fatty acids, which can be extracted following further treatment. As
presented in their review, research is being conducted toward biofuel generation from the
exploitation of coffee residues. Moreover, its capacity as a source of sugars, as absorbent
of pollutants and in particular heavy metals, and as a primary source for the production of
activated carbons are also being investigated.
At least 10–15% lipids, measured on a dry basis, have been found to remain in the used
coffee grounds. Different coffee residual biomass samples have been analyzed and approx-
imately 90% lipids were found to remain in the solid residue after coffee extraction. Spent
coffee biomass oil consists mainly of triglycerides and small amounts of diglycerides, free
fatty acids, terpenes, sterols, and tocopherols. Therefore, it represents an important source
of raw material for a variety of products including biofuels. Cholakov et al. (2013) applied
extraction methods on spent coffee grounds to evaluate their potential as a source of bio-
fuels and activated carbon absorbents. Their results were promising in both aspects but not
conclusive, so they recommended the need for further research. Coelho et al. (2018) exam-
ined the influence of three co-solvents, namely ethanol, isopropanol and ethyl lactate, on
the yield and composition of the oil extracted from the above spent coffee grounds. The
highest yield (12.4%) was obtained at a temperature of 333.2 K with 5% ethyl lactate as a
co-solvent (Georgieva et al. 2018).
A great proportion of the overall, worldwide spent coffee waste biomass production is
generated at the industrial sites where instant coffee is manufactured. Therefore, a further
treatment for added value compounds, for biofuels or any additional application will be free
of costs of collection and transportation of the raw material, and their management. The
weight that these costs carry in processes which target the valorization of waste biomass
constitute a major issue; they can be such that they can actually make or break the respec-
tive processes (Iervolino et al. 2018). Consequently, expansion of existing instant coffee
industries to incorporate processes for the extraction of added value compounds from the
remains of the spent coffee may be a venture worth considering.
2.2.2 Lignocellulose Biomass

Sindhu et al. (2016) present an overview of lignocellulosic biomass, which is high in cel-
lulose, hemicellulose, lignin and as such it can serve as an excellent source for biofuel
generation. And of course, an important virtue of this type of biomass is that it is renewable.
Second generation lignocellulosic biomass in particular, in addition to being an excellent
candidate for bioethanol production, is an amply available and low cost feedstock, which
is often accumulated in places favoring its treatment and as such, minimalizing the other-
wise high costs of transport and collection process as analyzed in the previous subsection
for spent coffee grounds. Such biomass can be the straw of cereals cultivated for human or
animal consumption, i.e. field residues or process residues such as residual biomass pro-
duced during the collection of wheat, rye, barley, oats, corn and other cereals, which are
traditionally used for animal feed, as natural absorbent of water, and as insulation mate-
rial in certain constructions. The collection of cereals takes place in the summer months
and as such this type of biomass can be collected in a dry form and can be transported to
biorefineries simultaneously with the collection of the edible crop. Such an option reduces
the management needs associated with the residual biomass collection. Husks of legumes,
rice and corns can be also used in a similar way and the same methods can be applied for
their collection. Additional source of lignocellulosic origin is the bagasse disposed of in
bioethanol production units, which with further treatment can produce additional biofu-
els. Moreover, they are readily available in the sites of bioethanol production and unless
they are further treated for further added value products generation, they form a waste
which has to be disposed of according to environmental requirements at additional costs
(Figure 2.3).
According to Eurostat, cereals in the EU are aiming to be used as food or food deriva-
tives by humans and/or animals. Cereals are extensively produced in Europe and all over the
world. During 2015 cereals and rice production in Europe reached around three hundred and
twenty million tons, half of which were different kinds of wheat and approximately 20%
Figure 2.3 Hay residues. Source: Truncated photo by Petar Starčević (https://www.pexels.com/photo/
hay-field-under-clear-sky-2389122).
was barley (KFE 2017). In addition to cereals, Europe cultivates plants with oil-generating
seeds, such as turnip-rape, rape, soya, and sunflower, the production of which was approx-
imately 30 million tons in 2016 with rapes accounting for two thirds of the quantity and
sunflower approaching one third. Soya production, which was only two and a half mil-
lion tons at the time, has increased (EAF&F 2017). These seeds are primarily used for oil
and/or bioethanol production. Therefore, the waste biomass produced after the treatment of
those seeds could always be further utilized for the extraction or formation of value-added
products, while appropriate further treatment can provide additional biofuels.
According to Zabed et al. (2016), the world availability of such biomass is approximately
three to four billion tons per year while 2–5 tons of such biomass could produce approx-
imately 1–2 m3 of ethanol. In their review, amongst others, they provide the content of
cereals of different origin (i.e. from rice or wheat, or barley or oat) in cellulose, hemicel-
lulose and lignin as measured by Saini et al. (2015), Ludueña et al. (2011) (rice husk), and
Sánchez (2009) (oat and rye straw).
Bioethanol production has well advanced over the last decade. The processes for its pro-
duction were designed to employ primary biomass produced for that very purpose. As such,
the composition and properties of the raw materials were assumed to be adequately similar.
However, the biomass properties are subject to numerous conditions such as variety of the
crop, season, temperature variations during growth, soil properties, irrigation frequency,
type of fertilizer and quantities used. Additionally, as these were industrial size continuous
processes, the constant supply of biomass of the same quantity and composition is of key
importance for their efficient operation which also ensures good and within the required
specification product quality (Abraham et al. 2016). Second generation biomass and gen-
erally waste biomass of a varying origin and composition will require inventive actions and
the design of processes versatile enough to adapt to the expected variations. This may be
proven a very challenging task. Abraham et al. (2016) discuss the potential of rice straw
as a second-generation source of biofuel so that this waste with a high annual volume can
be exploited. While this type of biomass can be used for the production of bioethanol, the
solid waste of the process can be further treated for the production of other type of biofuels.
The formation of biopolymers can also be feasible from this feedstock. According to Saini
et al. (2015), the annual universal production of rice residues is over 700 tons. Useful waste
biomass from rice straw consists of the rice stems, the leaf-sheaths and their blades. Much
research has been conducted on this waste biomass and data on its composition are available
in the literature.
Wheat straw is the residue of harvested wheat with an estimated annual yield of 1–3 tons
per acre. Talebnia et al. (2010) report research on wheat straw as a biofuel source. This
raw material, as many others of its kind, mainly contains cellulose (of strains very highly
attached to each other), hemicellulose and lignin in mass proportions of around one third
to 40% for the former, one fifth to one forth hemicellulose, and 15–20% for the latter, as
well as a smaller proportion of extractives. This kind of biomass resource is encountered
in ample quantities everywhere in the world. Those remains of agricultural produce after
all useful food parts have been collected can be exploited for direct bioethanol production
without the need for any additional investment. The United States alone generates over
400 million tons of biomass which comes from agricultural wastes usable for bioethanol
production, while an additional amount of approximately 0.4 billion tons of energy crops
is also available (Saini et al. 2015).
The production of corn, wheat, rice and sugar cane can provide the majority of agricul-
tural waste biomass which with appropriate management can form a precious raw material
for biofuel production (Kim and Dale 2004).
The production of biofuels from dedicated crops is straightforward because the employed
biomass composition is more or less the same. Waste biomass on the other hand has a wide
variability of composition. Consequently, its use as as an alternative feedstock for the pro-
duction of biofuels introduces several technical challenges. An effective way to resolve this
shortcoming is the implementation of appropriate pretreatment stages. Such stages can for
instance increase the biomass content in fermentable sugars. Alternatively, new fermen-
tation technologies can be developed to ensure viability and efficiency of the production
process (Sarkar et al. 2012).
Corn waste biomass, which consists of stalks and leaves, the empty cobs and the husks,
is a promising biomass for bioethanol production, because of its quantity (1 g per kg of
produced corn grains or about four tons of waste biomass per acre according to Kim and
Dale (2004)) and its composition (Sarkar et al. 2012).
A study conducted by Ayeni and Daramola (2017) considered the exploitation of corn
waste biomass for the production of biofuels and other products of everyday use. For that
purpose, they utilized different pretreatment methods involving, amongst others, alkaline
hydrolysis with or without hydrogen peroxide and dilute acid hydrolysis. They used these
processes in order to characterize the corncob, to enhance the cellulose, to remove the lignin,
to solubilize the hemicellulose and overall to evaluate the economics of the aforementioned
exploitation of this type of biomass on the basis of the above separations and characteri-
zations and they proposed methods which they demonstrated can ensure process viability
(Ayeni and Daramola 2017). Shariff et al. (2016) have also conducted research on corn-
cob residual biomass and in other kinds of feedstocks like palm wastes, rice husk, wheat
straw, wood sawdust, corncob (which is abundant in Malaysia throughout the year) for the
slow pyrolysis process. Corncob waste biomass was characterized for its cellulose, hemi-
celluloses and lignin content; the mass fractions of which were found to be approximately
0.46, 0.4, and over 0.11, respectively (Shariff et al. 2016). Corncob has low nitrogen and
Figure 2.4 Perennial plants.
sulfur contents and a high proportion of volatile matter, thus it was demonstrated that slow
pyrolysis is a suitable method for its valorization.
Bagasse from a multiplicity of processes can form an excellent feedstock for the gen-
eration of biofuels, simultaneously solving the environmental issues associated with their
disposal or cutting costs from their further treatment. According to Sánchez (2009), the
quantity of bagasse estimated at the time from all over the world was over a third of a mil-
lion tons. Similarly, perennial biomass can be exploited for the same objective (Mantziaris
et al. 2017). However, for both categories of these biomasses, the variation in quantity, qual-
ity (composition of feedstock) and availability of feedstock are posing new technological
challenges imposing the need for versatile and inventive approaches for their valorization.
At the same time however, they can act as a make-up feedstock to counterbalance seasonal
and compositional variations of biomass (Figure 2.4).
In summary, lignocellulosic residual biomass is abundant on the planet, it is of low cost
and often a waste which has to be environmentally disposed of, concentrated and accessi-
ble. It has a composition which is suitable for biofuel production; much research has been
conducted already and technology for its treatment is available.
2.2.3 Palm, Olive, Coconut, Avocado, and Argan Oil Production Residues
Edible oil production from trees serves the biofuel biomass supply in different ways. One
is that the oil production trees have a considerable life span and as such they are provid-
ing yearly biomass from pruning and leaves. The trees producing oily fruits have a smaller
but non-negligible content of oils in their leaves and branches; as such, the valorization of
residual biomass from trimmings toward biodiesel production in particular, is appropriate.
They are evergreen trees and as such they produce a continuous leaf supply. Their leaves
have valuable compounds, the extraction of which can be considered a means of improv-
ing the economics of processes, thus valorizing their residual biomass for biofuel. And, of
course, the used cooking oil resulting at a later stage is an excellent biodiesel source.
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And who will sit in Nóvgorod?”
There stepped forward Diví Murza, son of Ulán:
“Listen, our lord, Crimea’s tsar!
You, our lord, shall sit in stone-built Moscow,
And your son in Vladímir,
And your nephew in Súzdal,
And your relative in Zvenígorod,
And let the equerry hold old Ryazán,
But to me, O lord, grant Nóvgorod:
There, in Nóvgorod, lies my luck.”
The voice of the Lord called out from heaven:
“Listen, you dog, Crimea’s tsar!
Know you not the tsarate of Muscovy?
There are in Moscow seventy Apostles,[117]
Besides the three Sanctified;
And there is in Moscow still an orthodox Tsar.”
And you fled, you dog, Crimea’s tsar,
Not over the highways, nor the main road,
Nor following the black standard.
THE SONG OF THE PRINCESS KSÉNIYA BORÍSOVNA [118]
There weepeth a little bird,

A little white quail:
“Alas, that I so young must grieve!
They wish to burn the green oak,
To destroy my little nest,
To kill my little ones,
To catch me, quail.”
In Moscow the Princess weepeth:
“Alas that I so young must grieve!
For there comes to Moscow the traitor,
Gríshka Otrépev Rozstríga,[119]
Who wants to take me captive,
And having captured make me a nun,
To send me into the monastery.
But I do not wish to become a nun,
To go into a monastery:
I shall keep my dark cell open,
To look at the fine fellows.
O our beautiful corridors!
Who will walk over you
After our tsarian life
And after Borís Godunóv?
O our beautiful palace halls!
Who will be sitting in you
After our tsarian life
And after Borís Godunóv?”
And in Moscow the Princess weepeth,
The daughter of Borís Godunóv:
“O God, our merciful Saviour!
Wherefore is our tsardom perished,—
Is it for father’s sinning,
Or for mother’s not praying?
And you beloved palace halls!
Who will rule in you,
After our tsarian life?
Fine stuffs of drawn lace!—
Shall we wind you around the birches?
Fine gold-worked towels!
Shall we throw you into the woods?
Fine earrings of hyacinth
Shall we hang you on branches,
After our tsarian life,
After the reign of our father,
Glorious Borís Godunóv?
Wherefore comes to Moscow Rozstríga,
And wants to break down the palaces,
And to take me, princess, captive,
And to send me to Ustyúzhna Zheléznaya,
To make me, princess, a nun,
To place me behind a walled garden?
Why must I grieve,
As they take me to the dark cell,
And the abbess gives me her blessing?”
THE RETURN OF PATRIARCH FILARÉT TO MOSCOW[120]
The tsarate of Muscovy was happy

And all the holy Russian land.
Happy was the sovereign, the orthodox Tsar,
The Grand Duke Mikhaíl Fedórovich,
For he was told that his father had arrived,
His father Filarét Nikítich,
From the land of the infidel, from Lithuania.
He had brought back with him many princes and boyárs,
He had also brought the boyár of the Tsar,
Prince Mikhaíl Borísovich Sheyn.
There had come together many princes, boyárs, and dignitaries,
In the mighty tsarate of Muscovy:
They wished to meet Filarét Nikítich
Outside the famous stone-built Moscow.
’Tis not the red sun in its course,—
’Tis the orthodox Tsar that has gone out,
To meet his father dear,
Lord Filarét Nikítich.
With the Tsar went his uncle,
Iván Nikítich the boyár.—
“The Lord grant my father be well,
My father, lord Filarét Nikítich.”
They went not into the palace of the Tsar,
They went into the cathedral of the Most Holy Virgin,
To sing an honourable mass.
And he blessed his beloved child:
“God grant the orthodox Tsar be well,
Grand Duke Mikhaíl Fedórovich!
And for him to rule the tsarate of Muscovy
And the holy Russian land.
FOOTNOTES:
[116] Having destroyed almost the whole of Moscow by fire in

1572, Devlét-Giréy made again an incursion the next year. He
was so sure of an easy victory, that the streets of Moscow, so
Kúrbski tells, were alotted in advance to the Murzas. He came
with an army of 120,000 men, and left on the field of battle
100,000.
[117] Either churches or images of the apostles; a similar
interpretation holds for the next line.
[118] She was shorn a nun by order of the False Demetrius,
and was sent to a distant monastery.
[119] Rozstríga means “he who has abandoned his tonsure.”
[120] Filarét Nikítich, the father of Mikhaíl Fedórovich, returned
from his Lithuanian captivity in 1619 and was at once proclaimed
Patriarch.
Yúri Krizhánich. (1617-about 1677.)
Krizhánich was a Croatian who had studied at the Croatian
Seminary at Vienna, at the university of Bologna, and at the
Greek College of St. Athanasius at Rome, where he came in
contact with some Russians. He early dreamed of a union of
all the Slavic nations under the rule of Russia, and in 1657 he
went to Southern Russia, where he began a propaganda
among the Cossacks in favour of a union with that country.
Two years later he appeared in Moscow, where his Catholic
religion and his efforts at introducing a Western culture
brought him into disrepute, and he was at once banished to
Siberia, where he lived until the year 1676. He composed a
large number of works on an Universal Slavic language, on
the Russian empire in the seventeenth century, and on the
union of the Churches, writing not in Russian, but in a strange
mixture of several Slavic languages, of his own invention. In
these he developed a strong Panslavism, full of hatred of
everything foreign, except foreign culture, and expressed high
hopes for Russia’s future greatness. His works are said to
have been used by Peter the Great, but they were not
published until 1860.
POLITICAL REASONS FOR THE UNION OF THE CHURCHES
The sixth reason for my contention is of a political nature, and

refers to the nation’s weal. For this discord of the Churches is even
now the cause of Doroshénko’s rebellion and the Turkish invasion,
and continuation of the present war, and has from the beginning
been the cause of much evil. The Poles have an ancient adage: Aut
Moscovia Polonizat, aut Polonia Moscovizat, i. e., Either Moscow
shall become Polish, or Poland shall be a part of the Russian
empire. It is written in the histories of other nations, and the advisers
of the Tsar know it, that in the days of Feódor Ivánovich and later
there have been many congresses held and embassies sent for the
purpose of securing a Russian ruler for Poland and Lithuania. There
is no doubt but that Poland and Lithuania would have become
possessions of the Russian Tsars, if it were not for the division of the
Churches. And there would not have been many old and new wars,
nor bloodshed, in which so many hundreds of thousands of innocent
people have perished by the sword, and have been led into
Mussulman captivity. And the Russian nation would have long ago
been far advanced in profane and political sciences that are so
necessary for all well-educated persons, and would not be scorned
and ridiculed and hated by the European nations for its barbarism.
Nor would it suffer such unbearable disgrace and losses in war and
commerce from the Germans and Crimeans, as it is suffering now.
Book knowledge and political wisdom is a leaven of the mind, and a
fast friendship with the Poles and Lithuanians would have made the
Russian nation more renowned and more feared by the surrounding
peoples, and richer in all earthly possessions.
ON KNOWLEDGE
Kings must instruct their subjects, parents their children, how to

obtain knowledge. The time has come for our nation to be instructed
in various branches, for God has in His mercy and kindness uplifted
through Russia a Slavic kingdom to glory, power and majesty, such
as for splendour has never existed before among us. We observe
with other nations that as soon as a kingdom rises to higher
importance, the sciences and arts at once begin to flourish among
them. We, too, must learn, for under the honoured rule of the
Righteous Tsar and Great King Alexis Mikháylovich we have an
opportunity to wipe off the mould of our ancient barbarism, to acquire
various sciences, to adopt a better organisation of society, and to
reach a higher well-being.
ON FOREIGNERS
We are not possessed of an innate vivacity, nor praiseworthy

national characteristics, nor sincerity of heart. For people who have
such pride do not allow foreigners to command them, except by
force, whereas our nation of its own free will invites foreigners to
come to its country. Not one people under the sun has since the
beginning of the world been so abused and disgraced by foreigners
as we Slavs have been by the Germans. Our whole Slavic nation
has been subject to this kind of treatment; everywhere we have upon
our shoulders Germans, Jews, Scotchmen, Gypsies, Armenians,
Greeks and merchants of other nationalities, who suck our blood. In
Russia you will see nowhere any wealth, except in the Tsar’s
treasury; everywhere there is dire, bare poverty.
Grigóri Kotoshíkhin. (1630-1667.)
Grigóri Kotoshíkhin was a clerk, and later a scribe
(podyáchi) in the Department of Legations, a kind of Foreign
Office. He had been frequently employed as an ambassador
in connection with various treaties between Russia and
Sweden and Poland. While at Moscow, he had been guilty of
some dishonesty to his own country by giving certain secrets
of State to the Swedish ambassador; but that was an offence
not uncommon at Moscow, where patriotism was seldom of a
disinterested character. In 1664 he was sent out with the
Russian army that was then operating against Poland. Shortly
after, its two generals, Cherkásski and Prozoróvski, were
recalled, and Dolgorúki was sent in their place. The latter tried
to get Kotoshíkhin’s aid in denouncing his two predecessors
for traitorous actions, but Kotoshíkhin refused. Fearing the
wrath of Dolgorúki, he fled, first to Poland, and then, through
Prussia and Lubeck, to Sweden. He settled in Stockholm,
where he was employed in a semi-official capacity in the
Foreign Office. In a fit of intoxication he killed his host, who
was the official Russian translator of Sweden, and for this
crime he was beheaded.
Kotoshíkhin had evidently formed the plan of writing about
Russian customs before his arrival in Stockholm, but he was
also encouraged by distinguished Swedish statesmen, who
hoped to find important information about Russia in his work.
In his capacity of Legation scribe Kotoshíkhin had an
excellent opportunity to become intimately acquainted with
the immediate surroundings of the Tsar; but he supplemented
his knowledge by a clear insight, which he had gained in his
intercourse with other nations. There is no other work of Old
Russia that gives so detailed an account of contemporary
society. Kotoshíkhin’s work was first discovered in 1840,
though several manuscript translations in Swedish were
known to be extant in various libraries.
THE EDUCATION OF THE PRINCES
FROM CHAP. 1.
For the bringing up of the Tsarévich or Tsarévna they select from

among the women of all ranks a good, pure, sweet-tempered and
healthy woman, and that woman resides for a year in the Upper
Palace, in the apartments of the Tsarítsa. At the expiration of the
year, the husband of that woman, if she be of noble origin, is made
governor of a city, or receives some lands in perpetuity; if she be a
scribe’s, or some other serving-man’s wife, he is promoted and
granted a goodly salary; if he be a countryman, he is given a good
sum, and both are freed from the taxes and other imposts of the Tsar
during their whole lives. The Tsarévich and Tsarévna have also a
chief-nurse to look after them, a distinguished boyár’s wife,—an old
widow, and a nurse and other servants. When the Tsarévich reaches
the age of five, he is put in the keeping of a renowned boyár, a quiet
and wise man, and the latter has for a companion a man from the
lower ranks; they also choose from among the children of the boyárs
a few of the same age as the Tsarévich, to be his servants and
butlers. When the time arrives to teach the Tsarévich to read and
write, they select teachers from the instructed people, who are of a
quiet disposition and not given to drinking; the teacher of writing is
chosen from among the Legation scribes; they receive instruction in
Russia in no other language, neither Latin, Greek, German nor any
other, except Russian.
The Tsaréviches and Tsarévnas have each separate apartments
and servants to look after them. No one is permitted to see the
Tsarévich before his fifteenth year, except those people who serve
him, and the boyárs and Near People[121]; but after fifteen years he
is shown to all people, as his father goes with him to church or to
entertainments. When the people find out that he has been
presented, they come on purpose from many cities to get a look at
him. As the Tsaréviches, when they are young, and the elder and
younger Tsarévnas go to church, there are borne cloth screens all
around them, so that they cannot be seen; likewise, they cannot be
seen when they stand in church, except by the clergy, for they are
surrounded in church with taffeta, and there are few people in church
during that time but boyárs and Near People. Similarly, when they
travel to the monasteries to pray, their carriages are covered with
taffeta. For their winter rides, the Tsarítsa and Tsarévnas use
kaptánas, that is, sleighs in the shape of small huts that are covered
with velvet or red cloth, with doors at both sides, with mica windows
and taffeta curtains; for their summer rides they use kolymágas that
are also covered with cloth; these are entered by steps and are
made like simple carts on wheels, and not like carriages that hang
down on leather straps. These kolymágas and kaptánas have two
shafts, and are without an axle; only one horse is hitched in them,
with other horses in tandem.
PRIVATE LIFE OF THE BOYÁRS AND OF OTHER RANKS (CHAP. 13)
Boyárs and Near People live in their houses, both of stone and
wood, that are not well arranged; their wives and children live all in
separate rooms. Only a few of the greater boyárs have their own
churches in their courts; and those of the high and middle boyárs
who have no churches of their own, but who are permitted to have
priests at their houses, have the matins and vespers and other
prayers said in their own apartments, but they attend mass in any
church they may choose; they never have the mass in their own
houses. The boyárs and Near People pay their priests a yearly
salary, according to agreement; if the priests are married people,
they receive a monthly allowance of food and drink, but the widowed
priests eat at the same table with their boyárs.
On church holidays, and on other celebrations, such as name
days, birthdays and christenings, they frequently celebrate together.
It is their custom to prepare simple dishes, without seasoning,
without berries, or sugar, without pepper, ginger or other spices, and
they are little salted and without vinegar. They place on the table one
dish at a time; the other dishes are brought from the kitchen and are
held in the hands by the servants. The dishes that have little vinegar,
salt and pepper are seasoned at the table; there are in all fifty to one
hundred such dishes.
The table manners are as follows: before dinner the hosts order
their wives to come out and greet their guests. When the women
come, they place themselves in the hall, or room, where the guests
are dining, at the place of honour,[122] and the guests stand at the
door; the women greet the guests with the small salute,[123] but the
guests bow to the ground. Then the host makes a low obeisance to
his guests and bids them kiss his wife. At the request of his guests,
the host kisses his wife first; then the guests make individual bows
and, stepping forward, kiss his wife and, walking back again, bow to
her once more; she makes the small salute each time she kisses a
guest. Then the hostess brings each guest a glass of double-or
treble-spiced brandy, the size of the glass being a fourth, or a little
more, of a quart. The host makes as many low obeisances as there
are guests, asking each one in particular to partake of the brandy
which his wife is offering them. By the request of the guests, the host
bids his wife to drink first, then he drinks himself, and then the guests
are served; the guests make a low obeisance before drinking, and
also after they have drunk and as they return the glass. To those that
do not drink brandy, a cup of Rumney or Rhine wine, or some other
liquor, is offered.
After this drinking the hostess makes a bow to the guests and
retires to her apartments to meet her guests, the wives of the boyárs.
The hostess and the wives of the guests never dine with the men,
except at weddings; an exception is also made when the guests are
near relatives and there are no outsiders present at the dinner.
During the dinner, the host and guests drink after every course a cup
of brandy, or Rumney or Rhine wine, and spiced and pure beer, and
various kinds of meads. When they bring the round cakes to the
table, the host’s daughters-in-law, or married daughters, or the wives
of near relatives come into the room, and the guests rise and,
leaving the table, go to the door and salute the women; then the
husbands of the women salute them, and beg the guests to kiss their
wives and drink the wine they offer. The guests comply with their
request and return to the table, while the women go back to their
apartments. After dinner the host and guests drink more freely each
other’s healths, and drive home again. The boyárs’ wives dine and
drink in the same manner in their own apartments, where there are
no men present.
When a boyár or Near Man is about to marry off his son, or
himself, or a brother, or nephew, or daughter, or sister, or niece, he,
having found out where there is a marriageable girl, sends his
friends, men or women, to the father of that girl, to say that such and
such a one had sent them to inquire whether he would be willing to
give his daughter or relative to him or his relative, and what the girl’s
dowry would be in the trousseau, money, patrimony and serfs. If the
person addressed is willing to give him his daughter, or relative, he
replies to the inquiry that he intends to marry off the girl, only he has
to consider the matter with his wife and family, and that he will give a
definite answer on a certain day; but if he does not wish to give him
the girl, knowing that he is a drunkard, or fast, or has some other bad
habit, he will say at once that he will not give him the girl, or he will
find some excuse for refusing the request.
Having taken counsel with his wife and family, and having decided
to give him the girl, he makes a detailed list of her dowry, in money,
silver and other ware, dresses, patrimony and serfs, and sends it to
the people who had come to him from the prospective bridegroom,
and they, in their turn, take it to the bridegroom. Nothing is told of the
matter to the prospective bride, who remains in ignorance thereof.
The dowry of the bride appearing satisfactory, the groom sends his
people to the bride’s parents, to ask them to present the girl. The
bride’s parents reply that they are willing to show their daughter, only
not to the prospective groom, but to his father, mother, sister or near
female relative, in whom the groom may have special confidence.
On the appointed day the groom sends his mother or sister to
inspect the bride; the bride’s parents make preparations for that day,
attire their daughter in a fine garment, invite their relatives to dinner,
and seat their daughter at the table.
When the inspectress arrives, she is met with the honour due her,
and is placed at the table near the bride. Sitting at the table, the
inspectress converses with the girl on all kinds of subjects, in order
to try her mind and manner of speech, and closely watches her face,
eyes and special marks, in order to bring a correct report to the
bridegroom; having stayed a short time, she returns to the
bridegroom. If the inspectress takes no liking to the bride, having
discovered that she is silly, or homely, or has imperfect eyes, or is
lame, or a poor talker, and so reports to the groom, he gives her up,
and that is the last of it. But if the bride has found favour in the
inspectress’s eyes, and she tells the groom that the girl is good and
clever, and perfect in speech and all things, the groom sends his
former friends again to the girl’s parents, telling them that he likes
their daughter, and that he wishes to come to a parley to write the
marriage contract, in order to marry her on a certain date. The
bride’s parents send word to the groom through his trusted people
that he should come to the parley with a few of his friends in whom
he has most confidence on a certain day, in the forenoon or
afternoon.
On the appointed day the groom puts on his best clothes, and
drives with his father, or near relatives, or friends whom he loves
best to the bride’s parents. Upon arrival, the bride’s parents and her
near relatives meet them with due honour, after which they go into
the house and seat themselves according to rank. Having sat a
while, the groom’s father or other relative remarks that they have
come for the good work, as he has bid them; the host answers that
he is glad to see them, and that he is ready to take up the matter.
Then both sides begin to discuss all kinds of marriage articles and to
set the day for the wedding according to how soon they can get
ready for it, in a week, a month, half a year, a year, or even more.
Then they enter their names and the bride’s name and the names of
witnesses in the marriage contract, and it is agreed that he is to take
the girl on a certain date, without fail, and that the girl is to be turned
over to him on that date, without fail; and it is provided in that
contract that if the groom does not take the girl on the appointed day,
or the father will not give him his daughter on that day, the offending
party has to pay 1000, or 5000, or 10,000 roubles, as the agreement
may be. Having stayed a while, and having eaten and drunk, they
return home, without having seen the bride, and without the bride
having seen the groom; but the mother, or married sister, or wife of
some relative comes out to present the groom with some embroidery
from the bride.
If after that parley the groom finds out something prejudicial to the
bride, or someone interested in the groom tells him that she is deaf,
or mute, or maimed, or has some other bad characteristic, and the
groom does not want to take her,—and the parents of the bride
complain about it to the Patriarch that he has not taken the girl
according to the marriage articles, and does not want to take her,
and thus has dishonoured her; or the bride’s parents, having found
out about the groom that he is a drunkard, or diceplayer, or maimed,
or has done something bad, will not give him their daughter, and the
groom complains to the Patriarch,—the Patriarch institutes an
inquiry, and the fine is collected from the guilty party according to the
contract, and is given to the groom or bride, as the case may be; and
then both may marry whom they please.
But if both parties carry out their agreement, and get ready for the
wedding on the appointed day, then the groom invites to the wedding
his relatives and such other people as he likes, to be his ceremonial
guests, in the same manner as I described before about the Tsar’s
wedding[124]; on the part of the bride the guests are invited in the
same way. On the day of the wedding tables are set at the houses of
the groom and bride, and the word being given the groom that it is
time to fetch the bride, they all set out according to the ceremonial
rank: First the bread-men carry bread on a tray, then, if it be summer,
the priest with the cross rides on horseback, but in winter in a sleigh;
then follow the boyárs, the thousand-man, and the groom.
Having reached the court of the bride’s house, they enter the hall
in ceremonial order, and the bride’s father and his guests meet them
with due honour, and the order of the wedding is the same as
described in the Tsar’s wedding. When the time arrives to drive to
church to perform the marriage, the bride’smaids ask her parents to
give the groom and bride their blessing for the marriage. They bless
them with words, but before leaving bless them with a holy image,
and, taking their daughter’s hand, give her to the groom.
Then the ceremonial guests, the priest, and the groom with his
bride, whose hand he is holding, go out of the hall, and her parents
and their guests accompany them to the court; the groom places the
bride in a kolymága or kaptána, mounts a horse, or seats himself in
a sleigh; the ceremonial guests do likewise, and all drive to the
church where they are to be married. The bride’s parents and their
guests return to the hall, where they eat and drink until news is
brought from the groom; the bride is accompanied only by her own
and the bridegroom’s go-betweens. The two having been united, the
whole troop drives to the groom’s house, and news is sent to the
bride’s father that they have been propitiously married. When they
arrive at the groom’s court, the groom’s parents and their guests
meet them, and the parents, or those who are in their stead, bless
them with the images, and offer them bread and salt, and then all
seat themselves at the table and begin to eat, according to the
ceremony; and then the bride is unveiled.
The next morning the groom drives out with the bride’s-maid to call
the guests, those of his and the bride’s, to dinner. When he comes to
the bride’s parents, he thanks them for their having well brought up
their daughter, and for having given her to him in perfect health; after
having made the round to all the guests, he returns home. When all
the guests have arrived, the bride offers gifts to all the ceremonial
guests. Before dinner the groom goes with all the company to the
palace to make his obeisance to the Tsar. Having arrived in the
presence of the Tsar, all make a low obeisance, and the Tsar, without
taking off his cap, asks the married couple’s health. The groom bows
to the ground, and then the Tsar congratulates those who are united
in legitimate wedlock, and blesses the married pair with images, and
he presents them with forty sables, and for their garments a bolt of
velvet, and atlas, and gold-coloured silk, and calamanco, and simple
taffeta, and a silver vessel, a pound and a half to two pounds in
weight, to each of them; but the bride is not present at the audience.
Then the Tsar offers the thousand-man, and bridegroom, and the
ceremonial guests a cup of Rumney wine, and then a pitcher of
cherry wine, and after they have emptied their wine the Tsar
dismisses them.
After arriving home, they begin to eat and drink, and after the
dinner the parents and guests bless the married couple with images
and make them all kinds of presents, and after dinner the guests
drive home. On the third day, the bride and groom and the guests go
to dinner to the bride’s parents, with all their guests, and after the
dinner the bride’s parents and their guests make presents to the
married couple, and they drive home; and that is the end of the
festivity.
During the time that the groom is in the presence of the Tsar, the
bride sends in her name presents to the Tsarítsa and Tsarévnas,
tidies of taffeta, worked with gold and silver and pearls; the Tsarítsa
and Tsarévnas accept these gifts, and send to inquire about the
bride’s health.
During all the wedding festivities, no women are present, and
there is no music, except blowing of horns and beating of drums.
The proceeding is the same when a widowed daughter, or sister,
or niece is married off: the ceremonial and the festivity are the same.
In the beginning of the festivity, the priest who is to marry the pair
receives from the Patriarch and the authorities a permit, with the seal
attached to it, to marry them, having first ascertained that the bride
and groom are not related by sponsorship, nor by the ties of
consanguinity in the sixth and seventh generation, nor that he is the
husband of a fourth wife, nor she the wife of a fourth husband; but if
he discover that they are related by sponsorship, and so forth, he is
not allowed to marry them. Should the priest permit such an unlawful
marriage to take place, with his knowledge or without his knowledge,
he would be discharged from his priesthood and, if he was knowingly
guilty, he has to pay a big fine, and the authorities lock him up for a
year; but the married pair is divorced, without being fined, except the
sin which they have incurred, and if they have not been previously
married three times, they may marry again.
If a widower wants to marry a maiden, the ceremonial at the
wedding is the same, but during the wreathing in church the wreath
is placed on the groom’s right shoulder, whereas the bride wears her
wreath upon her head; if a widower for the third time marries a
maiden, the ceremonial is the same, but the wreath is placed on the
groom’s left shoulder, and the bride wears hers upon her head. The
same is done when a widow marries for the second or third time. But
when a widower marries for the second or third time a widow, then
there is no wreathing, and only a prayer is said instead of the
wreathing, and the wedding ceremonial is different from the one
mentioned above.
The manner of the parley, marriage and ceremonial wedding is the
same with the lower orders of the nobility as described above, and
the wedding is as sumptuous as they can afford to make it, but they
do not call upon the Tsar, except those of his retinue.
Among the merchants and peasants the parley and the ceremonial
are exactly the same, but they differ in their acts and dresses from
the nobility, each according to his means.
It sometimes happens that a father or mother has two or three
daughters, where the eldest daughter is maimed, being blind, or
lame, or deaf, or mute, while the other sisters are perfect in shape
and beauty and speech. When a man begins to sue for their
daughter, and he sends his mother, or sister, or someone else in
whom he has confidence to inspect her, the parents sometimes
substitute the second or third daughter for their maimed sister, giving
her the name of the latter, so that the inspectress, not knowing the
deceit, takes a liking to the girl and reports to the groom that she is a
proper person to marry. Then the groom, depending upon her words,
has a parley with the girl’s parents, that he is to marry her upon an
appointed day, and that the parents are to give her to him upon the
appointed day, and the fine is set so high that the guilty party is not
able to pay it. When the wedding takes place, the parents turn over
to him the maimed daughter, whose name is given in the articles of
marriage, but who is not the one the inspectresses had seen. But the
groom cannot discover on the wedding day that she is blind, or
disfigured, or has some other defect, or that she is deaf or mute, for
at the wedding she is veiled and does not say a word, nor can he
know whether she is lame, because her bride’smaids lead her under
her arms.
But in that case the man who has been deceived complains to the
Patriarch and authorities, and these take the articles of marriage and
institute an inquiry among the neighbours and housefolk, each one
individually, whether the person he had married is the one indicated
by name in the marriage articles. If so, the articles are valid, and no
faith is to be put in his contention, on the ground that it was his
business to be sure whom he was going to marry. But if the
neighbours and housefolk depose that the bride is not the same as
mentioned by name in the articles, the married pair is divorced, and
the parents have to pay a large fine and damages to the groom, and
besides the father is beaten with the knout, or his punishment is
even more severe, according to the Tsar’s will.
The same punishment is meted out to the man who presents his
serving maid or a widow in place of his unmarried daughter, by
giving her another name and dressing her up so as to look like his
daughter, or when his daughter is of short stature and they place her
on a high chair in such a way that her defect is not noticeable.
When parents have maimed or old daughters, and no one wants
to marry them, they are sent to a monastery to be shorn nuns.
When a man wants to inspect the bride himself, and the parents
grant the request, knowing that she is fair and that they need not be
ashamed of her, but the groom, having taken no liking to her, decries
her with damaging and injurious words, and thus keeps other suitors
away from her,—and the bride’s parents complain to the Patriarch or
authorities: these institute an inquiry, and having found the man
guilty, marry him to the girl by force; but if he has married another girl
before the complaint has been entered, the girl’s disgrace is taken
from her by an ukase.
When a man marries off his daughter or sister, and gives her a
large dowry in serfs and patrimony, and that daughter or sister,
having borne no children, or having borne some who have all died,
dies herself,—the dowry is all taken from her husband and is turned
over to those who had married her off. But if she leaves a son or
daughter, the dowry is, for the sake of her child, not taken from her
husband.
Gentle reader! Wonder not, it is nothing but the truth when I say
that nowhere in the whole world is there such deception practised
with marriageable girls as in the kingdom of Muscovy; there does not
exist there the custom, as in other countries, for the suitor to see and
sue for the bride himself.
The boyárs and Near People have in their houses 100, or 200, or
300, or 500, or 1000 servants, male and female, according to their
dignity and possessions. These servants receive a yearly salary, if
they are married, 2, 3, 5 or 10 roubles, according to their services,
and their wearing apparel, and a monthly allowance of bread and
victuals; they live in their own rooms in the court of the boyár’s
house. The best of these married servants are sent out by the
boyárs every year, by rotation, to their estates and villages, with the
order to collect from their peasants the taxes and rents. The
unmarried older servants receive some small wages, but the
younger ones receive nothing; all the unmarried servants get their
wearing apparel, hats, shirts and boots; the older of these servants
live in the farther lower apartments, and receive their food and drink
from the kitchen; on holidays they receive two cups of brandy each.
The female servants who are widows remain living in the houses of
their husbands, and they receive a yearly wage and a monthly
allowance of food; other widows and girls stay in the rooms of the
boyárs’ wives and daughters, and they receive their wearing apparel,
and their food from the boyár’s kitchen.
When these girls are grown up, the boyárs marry them, and also
the widows, to some one of their servants to whom they have taken
a liking, but sometimes by force. The wedding takes place in the
boyár’s hall, according to the rank of the marrying parties; the food
and festive dresses are furnished by the boyár. The girls are never
married to any person outside the boyár’s court, because both male
and female servants are his perpetual serfs. In the boyár’s house
there is an office for all domestic affairs, where an account is kept of
income and expenses, and all the affairs of the servants and
peasants are investigated and settled.
FOOTNOTES:
[121] A division of nobility below the boyárs.

[122] In the front corner, under the holy images.
[123] Bending as far as the girdle.
[124] “The wedding ceremony is as follows: on the Tsar’s side
the first order is the father and mother, or those who are in place
of his parents; the second order, the travellers,—the chief priest
with the cross, the thousand-man, who is a great personage in
that procession, and then the Tsar: eight boyárs. The duties of the
travellers are as follows: they stay with the Tsar and Tsarítsa at
the crowning in church, and at the table occupy higher places
than the others; the friends (drúzhka), whose duty it is to call the
guests to the wedding, to make speeches at the wedding in the
name of the thousand-man and Tsar, and to carry presents; the
bride’s maids (svákha) whose duty it is to watch the Tsarítsa, to
dress her and undress her; the candleholder, who holds the
candle when they get the Tsarítsa ready for the crowning; the
breadholders, who carry the bread on litters to and from church
(these litters are covered with gold velvet and embroidered cloth
and sable furs); the equerry with his suite. The third order is the
sitting boyárs, twelve men and twelve women, who sit as guests
at the tables, with the Tsar’s parents, but do not go to church with
the Tsar. The fourth order is of the court, who attend to the food
and drink.”

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Process Systems Engineering for

Biofuels Development Adrian

Titles in the Series:

GADE PANDU RANGAIAH

Limit of Liability/Disclaimer of Warranty

Library of Congress Cataloging-in-Publication Data

Names: Bonilla-Petriciolet, Adrián, editor. | Rangaiah, Gade Pandu, editor.

Title: Process systems engineering for biofuels development / edited by

Cover Design: Wiley

Set in 10/12pt, TimesLTStd by SPi Global, Chennai, India.

2 Waste Biomass Suitable as Feedstock for Biofuels Production 15

2.2.6 Waste Oil and Cooking Oil 37

3 Multiscale Analysis for the Exploitation of Bioresources: From Reactor

4 Challenges in the Modeling of Thermodynamic Properties and Phase

4.6 Challenges for the Biofuels Process Design Methods 109

5 Up-grading of Waste Oil: A Key Step in the Future of Biofuel

6 Production of Biojet Fuel from Waste Raw Materials: A Review 149

7 Computer-Aided Design for Genetic Modulation to Improve Biofuel

7.2.4 Regulatory On-Off Minimization 177

8 Implementation of Biodiesel Production Process Using

9 Process Analysis of Biodiesel Production – Kinetic Modeling,

9.3.2 Experimental Reaction Data Regression 234

10 Process Development, Design and Analysis of Microalgal Biodiesel

11 Thermochemical Processes for the Transformation of Biomass into

11.5 Liquefaction 296

12 Intensified Purification Alternative for Methyl Ethyl Ketone

13 Present and Future of Biofuels 341

Luiz Fernando de Lima Luz Junior Department of Chemical Engineering, Federal

1.1 Importance of Biofuels and Overview of their Production

Process Systems Engineering for Biofuels Development, First Edition.

Type of biofuels according to their processing routes

Source: Raud et al. 2019. Reproduced with permission of Elsevier.

1.2 Significance of Process Systems Engineering for Biofuels Production

1.2.1 Modeling of Physicochemical Properties of Thermodynamic Systems Related

1.2.2 Intensification of the Biomass Transformation Routes for the Production

1.2.3 Computer-Aided Methodologies for Process Modeling, Design, Optimization,

anticipated regulations for environmental protection impose additional restrictions to

1.3 Overview of this Book

state of the art in the processing of triglyceride-containing wastes, lignocellulosic materials,

Eason, J.P. and Cremaschi, S. (2014). A multi-objective superstructure optimization approach to

Process Systems Engineering for Biofuels Development, First Edition.

replaced by smaller, specialized-goods production. Alternative methods of production that

2.1.2 Problem Definition

2.1.3 The Biomass Pool

Figure 2.1 Sugar canes. Source: Truncated photo from https://www.pexels.com/search/agricultural

2.2 Kinds of Feedstock

2.2.1 Spent Coffee Grounds

2.2.2 Lignocellulose Biomass

Figure 2.4 Perennial plants.

THE SONG OF THE PRINCESS KSÉNIYA BORÍSOVNA [118]

There weepeth a little bird,

THE RETURN OF PATRIARCH FILARÉT TO MOSCOW[120]

The tsarate of Muscovy was happy

[116] Having destroyed almost the whole of Moscow by fire in

POLITICAL REASONS FOR THE UNION OF THE CHURCHES

The sixth reason for my contention is of a political nature, and

Kings must instruct their subjects, parents their children, how to

We are not possessed of an innate vivacity, nor praiseworthy

For the bringing up of the Tsarévich or Tsarévna they select from

PRIVATE LIFE OF THE BOYÁRS AND OF OTHER RANKS (CHAP. 13)

[121] A division of nobility below the boyárs.

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